JP4803320B2 - Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same - Google Patents
Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same Download PDFInfo
- Publication number
- JP4803320B2 JP4803320B2 JP2010541623A JP2010541623A JP4803320B2 JP 4803320 B2 JP4803320 B2 JP 4803320B2 JP 2010541623 A JP2010541623 A JP 2010541623A JP 2010541623 A JP2010541623 A JP 2010541623A JP 4803320 B2 JP4803320 B2 JP 4803320B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- liquid crystal
- general formula
- crystal composition
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 192
- 150000001875 compounds Chemical class 0.000 title claims description 158
- 239000000203 mixture Substances 0.000 title claims description 104
- 125000004432 carbon atom Chemical group C* 0.000 claims description 101
- 125000000217 alkyl group Chemical group 0.000 claims description 56
- 125000001153 fluoro group Chemical group F* 0.000 claims description 53
- 229910052731 fluorine Inorganic materials 0.000 claims description 49
- -1 pyridine-2,5-diyl group Chemical group 0.000 claims description 46
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 43
- 125000003545 alkoxy group Chemical group 0.000 claims description 36
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 35
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 32
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 27
- 125000003342 alkenyl group Chemical group 0.000 claims description 26
- 229910052801 chlorine Inorganic materials 0.000 claims description 26
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 26
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 25
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 24
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims description 20
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 125000005451 3-fluoro-1,4-phenylene group Chemical group [H]C1=C([*:1])C([H])=C(F)C([*:2])=C1[H] 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000005653 3,5-difluoro-1,4-phenylene group Chemical group [H]C1=C(F)C([*:2])=C(F)C([H])=C1[*:1] 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 210000004027 cell Anatomy 0.000 description 57
- 238000006116 polymerization reaction Methods 0.000 description 32
- 238000001514 detection method Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 21
- 239000003505 polymerization initiator Substances 0.000 description 18
- 210000002858 crystal cell Anatomy 0.000 description 17
- 0 Cc1cc(*)c(*)c(*)c1 Chemical compound Cc1cc(*)c(*)c(*)c1 0.000 description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 16
- 229910052753 mercury Inorganic materials 0.000 description 16
- 239000010408 film Substances 0.000 description 15
- 238000002347 injection Methods 0.000 description 15
- 239000007924 injection Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000004642 Polyimide Substances 0.000 description 14
- 238000004587 chromatography analysis Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 229920001721 polyimide Polymers 0.000 description 14
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 239000012071 phase Substances 0.000 description 7
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 7
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 4
- 101100496114 Caenorhabditis elegans clc-2 gene Proteins 0.000 description 4
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004988 Nematic liquid crystal Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 description 2
- 101100328110 Arabidopsis thaliana CLC-A gene Proteins 0.000 description 2
- 101100113656 Caenorhabditis elegans clc-5 gene Proteins 0.000 description 2
- 101100274575 Caenorhabditis elegans clh-3 gene Proteins 0.000 description 2
- 102100034473 H(+)/Cl(-) exchange transporter 6 Human genes 0.000 description 2
- 102100028685 H(+)/Cl(-) exchange transporter 7 Human genes 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- 125000005450 2,3-difluoro-1,4-phenylene group Chemical group [H]C1=C([*:2])C(F)=C(F)C([*:1])=C1[H] 0.000 description 1
- 150000004786 2-naphthols Chemical class 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical class C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical class CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 150000003232 pyrogallols Chemical class 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
- C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
- C09K19/2014—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n-
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
- C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3411—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3411—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a three-membered ring
- C09K2019/3413—Three-membered member ring with oxygen(s), e.g. oxirane in fused, bridged or spiro ring systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K2019/3416—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a four-membered ring, e.g. oxetane
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
- C09K2019/3425—Six-membered ring with oxygen(s) in fused, bridged or spiro ring systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/139—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent
- G02F1/1393—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent the birefringence of the liquid crystal being electrically controlled, e.g. ECB-, DAP-, HAN-, PI-LC cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal Substances (AREA)
- Liquid Crystal (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
本発明は重合性化合物を含有する液晶組成物、更に当該液晶組成物を使用した液晶表示素子に関する。 The present invention relates to a liquid crystal composition containing a polymerizable compound, and further to a liquid crystal display device using the liquid crystal composition.
MVAモード液晶表示装置の製造において、重合可能なモノマーを含有している液晶材料を基板間に注入し、電圧を印加した状態でモノマーを重合して液晶分子の倒れる方向を記憶しておくという技術が導入された。しかし、モノマーを重合する際に使用する重合開始剤や重合が不十分なため残存してしまうモノマーが液晶表示素子に対して焼き付き等の不具合を惹き起こすという問題が生じていた。このため、このような液晶材料中のモノマーを重合することにより液晶配向能を付与した液晶表示素子の製造においては、重合開始剤を使用しなくとも重合し、重合工程によりモノマーが完全に消費されるような液晶組成物の開発が求められていた。更に、実際の使用にあたっては、モノマーと液晶材料が良好に相溶し重合後の配向性も要求レベルを満たす必要があった。 In the manufacture of MVA mode liquid crystal display devices, a technique in which a liquid crystal material containing a polymerizable monomer is injected between substrates, the monomer is polymerized in a state where a voltage is applied, and the direction in which the liquid crystal molecules fall is stored. Was introduced. However, there has been a problem that the polymerization initiator used when polymerizing the monomer and the monomer remaining due to insufficient polymerization cause problems such as image sticking to the liquid crystal display element. For this reason, in the production of a liquid crystal display element imparted with liquid crystal alignment ability by polymerizing monomers in such a liquid crystal material, polymerization is performed without using a polymerization initiator, and the monomers are completely consumed by the polymerization process. Development of such a liquid crystal composition has been demanded. Furthermore, in actual use, the monomer and the liquid crystal material are compatible with each other and the orientation after polymerization needs to satisfy the required level.
従来は、焼き付きを防止するために、1,4−フェニレン基等の構造を有する化合物を用いて作製した素子(特許文献1参照)や、ビアリール構造を有する化合物を用いた素子(特許文献2参照)が提案されていた。しかしながら、当該引用文献記載の重合性化合物では光重合開始剤が含まれていないと重合が進行しなかったり、あるいは未重合でモノマーが残存し、その残存物が液晶表示素子に悪影響を与える懸念があった。一方、エネルギー線により重合性化合物を重合させ、その後熱処理を行うことで焼き付きを防止する製造方法(特許文献3参照)が提案されているが、必ずしも完全に重合性化合物が重合される方法ではなく、上記の他の方法と同様に未重合残存物が液晶表示素子に悪影響を与える懸念があった。 Conventionally, in order to prevent burn-in, an element manufactured using a compound having a structure such as a 1,4-phenylene group (see Patent Document 1) or an element using a compound having a biaryl structure (see Patent Document 2) ) Was proposed. However, if the polymerizable compound described in the cited document does not contain a photopolymerization initiator, the polymerization does not proceed, or the monomer remains unpolymerized, and the residue may adversely affect the liquid crystal display device. there were. On the other hand, a manufacturing method (see Patent Document 3) is proposed in which a polymerizable compound is polymerized by energy rays and then heat treatment is performed to prevent seizure, but this is not necessarily a method in which the polymerizable compound is completely polymerized. As with the other methods described above, there was a concern that the unpolymerized residue adversely affects the liquid crystal display device.
本発明が解決しようとする課題は、光重合開始剤を使用せずに重合性化合物を重合させ該化合物が残存しない、あるいは極めて残存量が少なくなる重合性化合物含有液晶組成物を提供することにあり、そして、重合性化合物と液晶材料が良好に相溶し、重合後の配向性がより安定し、表示特性に不具合が起こらない重合性化合物含有液晶組成物を提供することにある。更には、重合性化合物含有液晶組成物が重合することにより液晶配向能が付与され表示性能が優れた液晶表示素子を提供することにある。 The problem to be solved by the present invention is to provide a polymerizable compound-containing liquid crystal composition in which a polymerizable compound is polymerized without using a photopolymerization initiator so that the compound does not remain or the remaining amount is extremely small. Another object is to provide a polymerizable compound-containing liquid crystal composition in which the polymerizable compound and the liquid crystal material are compatible with each other, the orientation after polymerization is more stable, and display characteristics are not impaired. Furthermore, it is providing the liquid crystal display element which the liquid crystal aligning ability was provided by polymerizing the polymeric compound containing liquid crystal composition, and was excellent in display performance.
本願発明者らは種々の重合性化合物及び種々の非重合性の液晶材料の検討を行った結果、特定の構造を有する重合性化合物及び液晶材料から成る液晶組成物が前述の課題を解決できることを見出し本願発明を完成するに至った。 As a result of studying various polymerizable compounds and various non-polymerizable liquid crystal materials, the present inventors have found that a liquid crystal composition comprising a polymerizable compound having a specific structure and a liquid crystal material can solve the aforementioned problems. The headline of the present invention has been completed.
すなわち、第一成分として、一般式(I) That is, as the first component, the general formula (I)
(式中、R11は以下の式(R-1)から式(R-15)(In the formula, R 11 is the following formula (R-1) to formula (R-15)
の何れかを表し、
S11は、炭素原子数1〜12のアルキレン基、又は単結合を表し、該アルキレン基中のメチレン基は酸素原子同士が直接結合しないものとして酸素原子、−COO−、−OCO−、又は−OCOO−に置き換えられても良い、
Z11は、水素原子、フッ素原子、塩素原子、シアノ基、チオシアナト基、トリフルオロメトキシ基、トリフルオロメチル基、ジフルオロメトキシ基、又は炭素原子数1〜12のアルキル基を表し、該アルキル基中のメチレン基は酸素原子同士が直接結合しないものとして酸素原子、硫黄原子、−CO−、―COO−、−OCO−、−OCOO−、−CH=CH−、又は−C≡C−で置換されて良く、あるいはZ11は、−S12−R12
(式中、R12は独立してR11と同じ意味を表し、S12は独立してS11と同じ意味を表す。)を表し、
X11、X12、X13及びX14は、お互い独立して水素原子、アルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲン化アルコキシ基、ハロゲン、シアノ基、又はニトロ基を表し、
L11、L12、及びL14はお互い独立して、単結合、−O−、−S−、−CH2−、−OCH2−、−CH2O−、−CO−、−C2H4−、―COO−、−OCO−、−OCOOCH2−、−CH2OCOO−、−CO−NRa−、−NRa−CO−、−SCH2−、−CH2S−、―CH=CH−COO−、−COO―CH=CH−、−OCO−CH=CH−、−CH=CH−OCO−、―COOC2H4−、―OCOC2H4−、―C2H4OCO−、―C2H4COO−、−OCOCH2−、―CH2COO−、−CH=CH−、−CF=CH−、−CH=CF−、−CF2−、−CF2O−、−OCF2−、−CF2CH2−、−CH2CF2−、−CF2CF2−又は−C≡C−を表し(式中、Raは炭素原子数1〜4のアルキル基を表す。)、
L13は、―CH=CH−COO−、―CH=CH−OCO−、―COO−CH=CH−又は―OCO−CH=CH−を表し、
M11、及びM12は、お互い独立して1,4−フェニレン基、1,4−シクロヘキシレン基、ピリジン−2,5−ジイル基、ピリミジン−2,5−ジイル基、ピペリジン−2,5−ジイル基、ナフタレン−2,6−ジイル基、インダン−2,5−ジイル基、テトラヒドロナフタレン−2,6−ジイル基又は1,3−ジオキサン−2,5−ジイル基を表し、M11、M12は、お互い独立して無置換であるか又はこれらの基中に含まれる水素原子がフッ素原子、塩素原子、シアノ基、又は炭素原子数1〜8のアルキル基、ハロゲン化アルキル基、ハロゲン化アルコキシ基、アルコキシ基、又はニトロ基に置換されていても良く、
mは0又は1を表し、nは、1、2又は3を表し、nが2又は3を表す場合、2個又は3個存在するM12は同一であっても異なっていても良く、2個又は3個存在するL14は同一であっても異なっていても良い。)で表される重合性化合物から選ばれる一種又は二種以上の化合物を含有し、第二成分として、一般式(II)Any one of
S 11 represents an alkylene group having 1 to 12 carbon atoms or a single bond, and the methylene group in the alkylene group is an oxygen atom, —COO—, —OCO—, or — May be replaced by OCOO-,
Z 11 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, or an alkyl group having 1 to 12 carbon atoms, The methylene group is substituted with an oxygen atom, a sulfur atom, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C—, as oxygen atoms are not directly bonded to each other. Or Z 11 may be -S 12 -R 12
(Wherein R 12 independently represents the same meaning as R 11, and S 12 independently represents the same meaning as S 11 ),
X 11 , X 12 , X 13 and X 14 each independently represent a hydrogen atom, an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen, a cyano group, or a nitro group,
L 11 , L 12 , and L 14 are each independently a single bond, —O—, —S—, —CH 2 —, —OCH 2 —, —CH 2 O—, —CO—, —C 2 H. 4 -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - COO- CH = CH -, - OCO-CH = CH -, - CH = CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO- , —C 2 H 4 COO—, —OCOCH 2 —, —CH 2 COO—, —CH═CH—, —CF═CH—, —CH═CF—, —CF 2 —, —CF 2 O—, — OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 - or -C≡ - it represents, (wherein, R a represents an alkyl group having 1 to 4 carbon atoms.)
L 13 represents —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH— or —OCO—CH═CH—,
M 11 and M 12 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, piperidine-2,5. -Represents a diyl group, a naphthalene-2,6-diyl group, an indan-2,5-diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, M 11 , M 12 is independently substituted with each other, or a hydrogen atom contained in these groups is a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group, a halogen atom Substituted with an alkoxy group, an alkoxy group, or a nitro group,
m represents 0 or 1, n represents 1, 2 or 3, and when n represents 2 or 3, two or three M 12 may be the same or different. One or three L 14 may be the same or different. ) Containing one or more compounds selected from the polymerizable compounds represented by formula (II) as the second component
(式中、R21及びR22はお互い独立して炭素原子数1から10のアルキル基又は炭素原子数2から10のアルケニル基を表し、これらの基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置換されても良く、またこれらの基中に存在する1個又は2個以上の水素原子はフッ素原子又は塩素原子に置換されても良く、
M21、M22及びM23はお互い独立して
(a) トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置き換えられてもよい)、
(b) 1,4-フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は窒素原子に置き換えられてもよい)、3-フルオロ-1,4-フェニレン基、3,5-ジフルオロ-1,4-フェニレン基及び
(c) 1,4-シクロヘキセニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ピペリジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基及び1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基
からなる群より選ばれる基を表し、
oは0、1又は2を表し、
L21、及びL22はお互い独立して単結合、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−、−CH=CH−、−CH=N−N=CH−又は−C≡C−を表し、L22が複数存在する場合は、同一でも良く異なっていても良く、M23が複数存在する場合は、同一でも良く異なっていても良い。)で表される化合物を一種又は二種以上含有し、第三成分として、一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)(In the formula, R 21 and R 22 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one methylene group or an adjacent group present in these groups) Two or more methylene groups which are not present may be substituted with —O— or —S—, and one or more hydrogen atoms present in these groups are substituted with fluorine atoms or chlorine atoms. It ’s okay,
M 21 , M 22 and M 23 are independent of each other
(a) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by -O- or -S-) ),
(b) 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom), 3-fluoro-1 , 4-phenylene group, 3,5-difluoro-1,4-phenylene group and
(c) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 -Represents a group selected from the group consisting of -diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group,
o represents 0, 1 or 2;
L 21 and L 22 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— , —CH═CH—, —CH═N—N═CH— or —C≡C—, and when there are a plurality of L 22 s , they may be the same or different, and there are a plurality of M 23 s. May be the same or different. 1 or 2 or more compounds represented by general formula (IIIa), general formula (IIIb) and general formula (IIIc)
(式中R31、R32及びR33はお互い独立して炭素原子数1から10のアルキル基又は炭素原子数2から10のアルケニル基を表し、これらの基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置換されても良く、またこれらの基中に存在する1個又は2個以上の水素原子はフッ素原子又は塩素原子に置換されても良く、
M31、M32、M33、M34、M35、M36、M37、及びM38はお互い独立して、
(d) トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置き換えられてもよい)、
(e) 1,4-フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は窒素原子に置き換えられてもよい)、3-フルオロ-1,4-フェニレン基、3,5-ジフルオロ-1,4-フェニレン基、及び、
(f) 1,4-シクロヘキセニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ピペリジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基及びデカヒドロナフタレン-2,6-ジイル基
からなる群より選ばれる基であり、上記の基(d)、基(e)又は基(f)に含まれる水素原子はそれぞれシアノ基、フッ素原子、トリフルオロメチル基、トリフルオロメトキシ基又は塩素原子で置換されていても良く、
L31、L32、L33、L34、L35、L36、L37及びL38はお互い独立して単結合、−COO−、−OCO−、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−又は−C≡C−を表し、M32、M34、M35、M37、M38、L31、L33、L35、L36、及び/又はL38が複数存在する場合は、それらは同一でも良く異なっていても良く、
X31、X32、X33、X34、X35、X36、及びX37はお互い独立して水素原子又はフッ素原子を表し、
Y31、Y32、及びY33はお互い独立して水素原子、フッ素原子、塩素原子、シアノ基、チオシアナト基、トリフルオロメトキシ基、トリフルオロメチル基、2,2,2-トリフルオロエチル基、又はジフルオロメトキシ基を表し、
X31、X32、又はY31のうち少なくともひとつはフッ素原子、塩素原子、シアノ基、チオシアナト基、トリフルオロメトキシ基、トリフルオロメチル基、2,2,2-トリフルオロエチル基、又はジフルオロメトキシ基を表すか、M31、又はM32、に含まれる水素原子のうち少なくともひとつはシアノ基、フッ素原子、トリフルオロメチル基、トリフルオロメトキシ基又は塩素原子を表し、
X33、X34、X35、又はY32のうち少なくともひとつはフッ素原子、塩素原子、シアノ基、チオシアナト基、トリフルオロメトキシ基、トリフルオロメチル基、2,2,2-トリフルオロエチル基、ジフルオロメトキシ基を表すか、M33、M34、又はM35、に含まれる水素原子のうち少なくともひとつはシアノ基、フッ素原子、トリフルオロメチル基、トリフルオロメトキシ基又は塩素原子を表し、
X36、X37、又はY33のうち少なくともひとつはフッ素原子、塩素原子、シアノ基、チオシアナト基、トリフルオロメトキシ基、トリフルオロメチル基、2,2,2-トリフルオロエチル基、ジフルオロメトキシ基を表すか、M36、M37、及びM38、に含まれる水素原子のうち少なくともひとつはシアノ基、フッ素原子、トリフルオロメチル基、トリフルオロメトキシ基又は塩素原子を表し、
p、q、r、s、及びtはお互い独立して、0、1又は2を表すが、q+r及びs+tは2以下である。)で表される化合物からなる群から選ばれる化合物又は
一般式(IVa)、一般式(IVb)及び一般式(IVc)(Wherein R 31 , R 32 and R 33 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one methylene group present in these groups) Alternatively, two or more methylene groups that are not adjacent to each other may be substituted with -O- or -S-, and one or more hydrogen atoms present in these groups may be replaced with a fluorine atom or a chlorine atom. May be replaced,
M 31 , M 32 , M 33 , M 34 , M 35 , M 36 , M 37 , and M 38 are independent of each other,
(d) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by -O- or -S-) ),
(e) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom), 3-fluoro-1 , 4-phenylene group, 3,5-difluoro-1,4-phenylene group, and
(f) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3,4 -A group selected from the group consisting of a tetrahydronaphthalene-2,6-diyl group and a decahydronaphthalene-2,6-diyl group, and is included in the above group (d), group (e) or group (f) Each hydrogen atom may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
L 31 , L 32 , L 33 , L 34 , L 35 , L 36 , L 37 and L 38 are each independently a single bond, —COO—, —OCO—, —CH 2 CH 2 —, — (CH 2 ) 4 -, - OCH 2 - , - CH 2 O -, - OCF 2 -, - CF 2 O- or represents -C≡C-, M 32, M 34, M 35, M 37, M 38, L 31 , L 33 , L 35 , L 36 , and / or a plurality of L 38 , they may be the same or different,
X 31 , X 32 , X 33 , X 34 , X 35 , X 36 , and X 37 each independently represent a hydrogen atom or a fluorine atom,
Y 31 , Y 32 and Y 33 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, Or a difluoromethoxy group,
At least one of X 31 , X 32 , and Y 31 is a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, or a difluoromethoxy. Or at least one of the hydrogen atoms contained in M 31 or M 32 represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, or a chlorine atom,
At least one of X 33 , X 34 , X 35 , or Y 32 is a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, A difluoromethoxy group, or at least one of hydrogen atoms contained in M 33 , M 34 , or M 35 represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, or a chlorine atom,
At least one of X 36 , X 37 and Y 33 is a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a difluoromethoxy group Or at least one of the hydrogen atoms contained in M 36 , M 37 and M 38 represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
p, q, r, s, and t independently represent 0, 1, or 2, but q + r and s + t are 2 or less. Or a compound selected from the group consisting of compounds represented by formula (IVa), general formula (IVb) and general formula (IVc)
(式中R41、R42、R43、R44、R45及び、R46はお互い独立して炭素原子数1から10のアルキル基又は炭素原子数2から10のアルケニル基を表し、これらの基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置換されていても良く、またこれらの基中に存在する1個又は2個以上の水素原子はフッ素原子又は塩素原子に置換されても良く、
M41、M42、M43、M44、M45、M46、M47、M48、及びM49はお互い独立して、
(d) トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置き換えられてもよい)、
(e) 1,4-フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は窒素原子に置き換えられてもよい)及び、
(f) 1,4-シクロヘキセニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ピペリジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基及びデカヒドロナフタレン-2,6-ジイル基
からなる群より選ばれる基であり、上記の基(d)、基(e)又は基(f)に含まれる水素原子はそれぞれシアノ基、フッ素原子、トリフルオロメチル基、トリフルオロメトキシ基又は塩素原子で置換されていても良く、
L41、L42、L43、L44、L45、L46、L47、L48、及びL49はお互い独立して単結合、−COO−、−OCO−、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−又は−C≡C−を表し、M42、M43、M45、M46、M48、M49、L41、L43、L44、L46、L47及び/又はL49が複数存在する場合は、それらは同一でも良く異なっていても良く、
X41、X42はお互い独立してトリフルオロメチル基、トリフルオロメトキシ基又はフッ素原子を表し、X43、X44、X45、X46、X47、及びX48はお互い独立して水素原子、トリフルオロメチル基、トリフルオロメトキシ基又はフッ素原子を表すが、X41及びX42の何れか一つはフッ素原子を表し、X43、X44、及びX45の何れか一つはフッ素原子を表し、X46、X47、及びX48の何れか一つはフッ素原子を表すが、X46、及びX47、は同時にフッ素原子を表すことはなく、X46、及びX48は同時にフッ素原子を表すことはない、
Gはメチレン基又は−O−を表し、
u、v、w、x、y、及びzはお互い独立して、0、1又は2を表すが、u+v、w+x及びy+zは2以下である。)で表される化合物からなる群から選ばれる化合物を一種又は二種以上含有することを特徴とする液晶組成物を提供し、更に、当該液晶組成物を用いた液晶表示素子を提供する。(Wherein R 41 , R 42 , R 43 , R 44 , R 45 and R 46 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and One methylene group present in the group or two or more methylene groups not adjacent to each other may be substituted with -O- or -S-, and one or two present in these groups The above hydrogen atoms may be substituted with fluorine atoms or chlorine atoms,
M 41 , M 42 , M 43 , M 44 , M 45 , M 46 , M 47 , M 48 , and M 49 are independent of each other.
(d) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by -O- or -S-) ),
(e) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom);
(f) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3,4 -A group selected from the group consisting of a tetrahydronaphthalene-2,6-diyl group and a decahydronaphthalene-2,6-diyl group, and is included in the above group (d), group (e) or group (f) Each hydrogen atom may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
L 41 , L 42 , L 43 , L 44 , L 45 , L 46 , L 47 , L 48 , and L 49 are each independently a single bond, —COO—, —OCO—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— or —C≡C— represents M 42 , M 43 , M 45 , M 46 , When there are a plurality of M 48 , M 49 , L 41 , L 43 , L 44 , L 46 , L 47 and / or L 49 , they may be the same or different,
X 41 and X 42 each independently represents a trifluoromethyl group, a trifluoromethoxy group or a fluorine atom, and X 43 , X 44 , X 45 , X 46 , X 47 and X 48 are each independently a hydrogen atom. , A trifluoromethyl group, a trifluoromethoxy group, or a fluorine atom, wherein any one of X 41 and X 42 represents a fluorine atom, and any one of X 43 , X 44 , and X 45 represents a fluorine atom Any one of X 46 , X 47 and X 48 represents a fluorine atom, but X 46 and X 47 do not represent a fluorine atom at the same time, and X 46 and X 48 represent fluorine at the same time. Never represent an atom,
G represents a methylene group or —O—;
u, v, w, x, y, and z each independently represent 0, 1, or 2, but u + v, w + x, and y + z are 2 or less. The liquid crystal composition characterized by containing 1 type, or 2 or more types of compounds chosen from the group which consists of a compound represented by this is provided, Furthermore, the liquid crystal display element using the said liquid crystal composition is provided.
本願発明の重合性化合物は他の液晶材料との相溶性が優れるため、安定した液晶組成物を得ることができる。また、該重合性化合物を含有する液晶組成物は、光重合開始剤を使用することなくあるいは少量の添加で重合性化合物を重合させることができ、重合後に残存する未重合の重合性化合物がない、あるいは極めて少ない。これにより液晶材料中の重合性化合物をポリマー化することで配向付与する液晶表示素子の表示不具合が大幅に軽減されるため、該液晶表示素子用の液晶材料として有用である。 Since the polymerizable compound of the present invention has excellent compatibility with other liquid crystal materials, a stable liquid crystal composition can be obtained. The liquid crystal composition containing the polymerizable compound can polymerize the polymerizable compound without using a photopolymerization initiator or with a small amount of addition, and there is no unpolymerized polymerizable compound remaining after polymerization. Or very little. Since the display defect of the liquid crystal display element which provides alignment by polymerizing the polymerizable compound in the liquid crystal material is thereby greatly reduced, it is useful as a liquid crystal material for the liquid crystal display element.
本願発明の重合性化合物を含有する液晶組成物で用いられる重合性化合物は、一般式(I)で表される化合物で構成される。一般式(I)において、R11は重合基を表すが、重合性基の具体的な例としては、下記に示す構造が挙げられる。The polymerizable compound used in the liquid crystal composition containing the polymerizable compound of the present invention is composed of a compound represented by the general formula (I). In the general formula (I), R 11 represents a polymerizable group, and specific examples of the polymerizable group include the structures shown below.
これらの重合基はラジカル重合、ラジカル付加重合、カチオン重合、及びアニオン重合により硬化する。特に重合方法として紫外線重合を行う場合には、式(R−1)、式(R−2)、式(R−4)、式(R−5)、式(R−7)、式(R−11)、式(R−13)又は式(R−15)が好ましく、式(R−1)、式(R−2)、式(R−7)、式(R−11)又は式(R−13)がより好ましく、式(R−1)、式(R−2)がより好ましい。 These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when performing ultraviolet polymerization as a polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R -11), formula (R-13) or formula (R-15) are preferred, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferable, and formula (R-1) and formula (R-2) are more preferable.
S11は、スペーサー基又は単結合を表すが、スペーサー基としては、炭素原子数1〜12のアルキレン基、又は単結合が好ましく、該アルキレン基中のメチレン基は酸素原子同士が直接結合しないものとして酸素原子、−COO−、−OCO−、又は−OCOO−に置き換えられても良い。S 11 represents a spacer group or a single bond, and the spacer group is preferably an alkylene group having 1 to 12 carbon atoms or a single bond, and the methylene group in the alkylene group does not directly bond oxygen atoms to each other. As an oxygen atom, -COO-, -OCO-, or -OCOO-.
Z11は、水素原子、フッ素原子、塩素原子、シアノ基、チオシアナト基、トリフルオロメトキシ基、トリフルオロメチル基、ジフルオロメトキシ基、メチレン基は酸素原子同士が直接結合しないものとして酸素原子、硫黄原子、−CO−、―COO−、−OCO−、−OCOO−、−CH=CH−、又は−C≡C−で置換されて良い炭素原子数1〜12のアルキル基、又は−S12−R12が好ましく、水素原子、フッ素原子、メチレン基が酸素原子同士が直接結合しないものとして酸素原子、−CO−、―COO−、−OCO−、又は−OCO−で置換されて良い炭素原子数1〜12のアルキル基、又は−S12−R12がより好ましく、メチレン基が酸素原子同士が直接結合しないものとして酸素原子で置換されて良い炭素原子数1〜12のアルキル基、又は−S12−R12がより好ましい。R12は独立してR11と同じ意味を表し、S12は独立してS11と同じ意味を表す。Z11が、−S12−R12の場合、S11及びS12は、上記同様にお互い独立してスペーサー基又は単結合を表すが、スペーサー基としては、炭素原子数2〜12のアルキレン基、又は単結合が好ましく、メチレン基は酸素原子同士が直接結合しないものとして酸素原子、−COO−、−OCO−、又は−OCOO−に置き換えられても良い炭素原子数2〜12のアルキレン基、又は単結合が好ましく、少なくとも一方が、メチレン基は酸素原子同士が直接結合しないものとして酸素原子、−COO−、−OCO−、又は−OCOO−に置き換えられても良い炭素原子数2〜12のアルキレン基がより好ましい。Z 11 is a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, or a methylene group, in which oxygen atoms are not directly bonded to each other. , —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, or an alkyl group having 1 to 12 carbon atoms which may be substituted with —C≡C—, or —S 12 —R 12 is preferable, and the number of carbon atoms that may be substituted with an oxygen atom, —CO—, —COO—, —OCO—, or —OCO— as a hydrogen atom, a fluorine atom, or a methylene group in which oxygen atoms are not directly bonded to each other To 12 alkyl groups, or —S 12 —R 12 is more preferable, and the number of carbon atoms that may be substituted with an oxygen atom as a methylene group in which oxygen atoms are not directly bonded to each other 1-12 alkyl group, or -S 12 -R 12 are more preferred. R 12 independently represents the same meaning as R 11, and S 12 independently represents the same meaning as S 11 . When Z 11 is —S 12 —R 12 , S 11 and S 12 each independently represent a spacer group or a single bond, and the spacer group is an alkylene group having 2 to 12 carbon atoms. Or a single bond is preferable, and a methylene group is an alkylene group having 2 to 12 carbon atoms which may be replaced by an oxygen atom, -COO-, -OCO-, or -OCOO- as a group in which oxygen atoms are not directly bonded to each other, Alternatively, a single bond is preferable, and at least one of the methylene groups has 2 to 12 carbon atoms which may be replaced with an oxygen atom, —COO—, —OCO—, or —OCOO—, as oxygen atoms are not directly bonded to each other. An alkylene group is more preferred.
X11、X12、X13及びX14は、お互い独立して水素原子、アルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲン化アルコキシ基、ハロゲン、シアノ基、又はニトロ基が好ましく、水素原子、アルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲン化アルコキシ基、又はハロゲンがより好ましく、水素原子、アルキル基、アルコキシ基、又はハロゲンがより好ましい。X 11 , X 12 , X 13 and X 14 are each independently preferably a hydrogen atom, an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen, a cyano group or a nitro group, An alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, or a halogen is more preferable, and a hydrogen atom, an alkyl group, an alkoxy group, or a halogen is more preferable.
L11、L12、及びL14はお互い独立して、単結合、−O−、−S−、−CH2−、−OCH2−、−CH2O−、−CO−、−C2H4−、―COO−、−OCO−、−OCOOCH2−、−CH2OCOO−、−CO−NRa−、−NRa−CO−、−SCH2−、−CH2S−、―CH=CH−COO−、−COO―CH=CH−、−OCO−CH=CH−OCO−、−CH=CH−、―COOC2H4−、―OCOC2H4−、―C2H4OCO−、―C2H4COO−、−OCOCH2−、―CH2COO−、−CH=CH−、−CF=CH−、−CH=CF−、−CF2−、−CF2O−、−OCF2−、−CF2CH2−、−CH2CF2−、−CF2CF2−又は−C≡C−が好ましく(式中、Raは炭素原子数1〜4のアルキル基を表す。)、単結合、−O−、−OCH2−、−CH2O−、−CO−、−C2H4−、―COO−、−OCO−、−OCOOCH2−、−CH2OCOO−、―CH=CH−COO−、−COO―CH=CH−、−OCO−CH=CH−OCO−、―COOC2H4−、―OCOC2H4−、―C2H4OCO−、―C2H4COO−、−OCOCH2−、―CH2COO−、又は−CH=CH−がより好ましく、単結合、−O−、−OCH2−、−CH2O−、―CH=CH−COO−、−COO―CH=CH−、−OCO−CH=CH−OCO−、―COOC2H4−、―OCOC2H4−、―C2H4OCO−、―C2H4COO−、−OCOCH2−、―CH2COO−、又は−CH=CH−がより好ましい。L 11 , L 12 , and L 14 are each independently a single bond, —O—, —S—, —CH 2 —, —OCH 2 —, —CH 2 O—, —CO—, —C 2 H. 4 -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - COO- CH = CH -, - OCO-CH = CH-OCO -, - CH = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO- , —C 2 H 4 COO—, —OCOCH 2 —, —CH 2 COO—, —CH═CH—, —CF═CH—, —CH═CF—, —CF 2 —, —CF 2 O—, — OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 - or -C≡ - is preferably (wherein, R a represents an alkyl group having 1 to 4 carbon atoms.), A single bond, -O -, - OCH 2 - , - CH 2 O -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CH = CH-COO -, - COO-CH = CH -, - OCO-CH = CH-OCO -, - COOC 2 H 4 —, —OCOC 2 H 4 —, —C 2 H 4 OCO—, —C 2 H 4 COO—, —OCOCH 2 —, —CH 2 COO—, or —CH═CH— are more preferable. Bond, —O—, —OCH 2 —, —CH 2 O—, —CH═CH—COO—, —COO—CH═CH—, —OCO—CH═CH—OCO—, —COOC 2 H 4 —, -OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO- -OCOCH 2 -, - CH 2 COO- , or -CH = CH- is more preferable.
L13は、―CH=CH−COO−、―CH=CH−OCO−、―COO−CH=CH−、又は―OCO−CH=CH−が好ましく、―CH=CH−COO−、又は―OCO−CH=CH−がより好ましい。L 13 is preferably —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, or —OCO—CH═CH—, —CH═CH—COO—, or —OCO -CH = CH- is more preferable.
M11、及びM12は、お互い独立して1,4−フェニレン基、1,4−シクロヘキシレン基、ピリジン−2,5−ジイル基、ピリミジン−2,5−ジイル基、ピペリジン−2,5−ジイル基、ナフタレン−2,6−ジイル基、インダン−2,5−ジイル基、テトラヒドロナフタレン−2,6−ジイル基又は1,3−ジオキサン−2,5−ジイル基が好ましく、1,4−フェニレン基、1,4−シクロヘキシレン基、ナフタレン−2,6−ジイル基、又はテトラヒドロナフタレン−2,6−ジイル基がより好ましく、1,4−フェニレン基、1,4−シクロヘキシレン基が特に好ましい。M11、M12は、これら基中に含まれる水素原子がお互い独立してフッ素原子、塩素原子、シアノ基、炭素原子数1〜8のアルキル基、ハロゲン化アルキル基、ハロゲン化アルコキシ基、アルコキシ基、ニトロ基に置換されているか、又は無置換であることが好ましく、フッ素原子、炭素原子数1〜8のアルキル基、アルコキシ基に置換されているか、又は無置換であることがより好ましく、フッ素原子に置換されているか、又は無置換であることが特に好ましい。M 11 and M 12 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, piperidine-2,5. A diyl group, a naphthalene-2,6-diyl group, an indane-2,5-diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, preferably 1,4 -Phenylene group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group, or tetrahydronaphthalene-2,6-diyl group is more preferred, and 1,4-phenylene group and 1,4-cyclohexylene group are preferred. Particularly preferred. In M 11 and M 12 , hydrogen atoms contained in these groups are each independently a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group, a halogenated alkoxy group, an alkoxy group. Group, substituted with a nitro group, or preferably unsubstituted, more preferably substituted with a fluorine atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or unsubstituted, It is particularly preferable that the fluorine atom is substituted or unsubstituted.
mは0又は1を表し、nは、1、2又は3を表す。nが2又は3を表す場合、2個又は3個存在するM12は同一であっても異なっていても良く、2個又は3個存在するL14は同一であっても異なっていても良い。
一般式(I)で表される化合物は、より具体的には、下記の一般式(I-1)〜(I-39)で表される化合物が好ましい。m represents 0 or 1, and n represents 1, 2 or 3. When n represents 2 or 3, two or three M 12 may be the same or different, and two or three L 14 may be the same or different. .
More specifically, the compounds represented by the general formula (I) are preferably compounds represented by the following general formulas (I-1) to (I-39).
更には、一般式(I-1)〜(I-30)及び(I-36)〜(I-39)で表される化合物が好ましい。 Furthermore, the compounds represented by the general formulas (I-1) to (I-30) and (I-36) to (I-39) are preferable.
本願発明の重合性化合物を含有する液晶組成物では、一般式(I)で表される重合性化合物を少なくとも1種を含有するが、1種〜5種含有することが好ましく、1種〜3種含有することが特に好ましく、一般式(I)で表される化合物の含有率の下限値は0.01質量%であることが好ましく、0.03質量%であることがより好ましく、上限値は2.0質量%であることが好ましく、1.0質量%であることがより好ましい。 The liquid crystal composition containing the polymerizable compound of the present invention contains at least one polymerizable compound represented by the general formula (I), preferably 1 to 5 types, preferably 1 to 3 types. It is particularly preferable to contain a seed, and the lower limit of the content of the compound represented by the general formula (I) is preferably 0.01% by mass, more preferably 0.03% by mass, and the upper limit. Is preferably 2.0% by mass, and more preferably 1.0% by mass.
第二成分として使用する一般式(II)で表される化合物において、R21及びR22はお互い独立して炭素原子数1から10のアルキル基又は炭素原子数2から10のアルケニル基(これらの基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置換されたもの、またこれらの基中に存在する1個又は2個以上の水素原子はフッ素原子又は塩素原子に置換されたものも含む。)が好ましく、炭素原子数1から5のアルキル基、炭素原子数1から5のアルコキシ基、炭素原子数2から5のアルケニル基又は炭素原子数3から6のアルケニルオキシ基がより好ましく、炭素原子数1から5のアルキル基又は炭素原子数1から5のアルコキシ基が特に好ましい。In the compound represented by the general formula (II) used as the second component, R 21 and R 22 are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms (these One methylene group present in a group or two or more methylene groups not adjacent to each other is substituted with -O- or -S-, and one or more methylene groups present in these groups The hydrogen atom includes those substituted with a fluorine atom or a chlorine atom.), Preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or An alkenyloxy group having 3 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is particularly preferable.
M21、M22及びM23はお互い独立してトランス-1,4-シクロヘキシレン基(この基中に存在する1個のCH2基又は隣接していない2個のCH2基が酸素原子に置換されているものを含む)、1,4-フェニレン基(この基中に存在する1個又は2個以上のCH基は窒素原子に置換されているものを含む)、3-フルオロ-1,4-フェニレン基、3,5-ジフルオロ-1,4-フェニレン基、1,4-シクロヘキセニレン基、1,4-ビシクロ[2.2.2]オクチレン基、ピペリジン-1,4-ジイル基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基又は1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基が好ましく、トランス-1,4-シクロヘキシレン基、1,4-フェニレン基、又は1,4-ビシクロ[2.2.2]オクチレン基を表すことがより好ましく、トランス-1,4-シクロヘキシレン基又は1,4-フェニレン基を表すことが特に好ましい。oは0、1又は2が好ましく、0又は1はより好ましい。L21、及びL22はお互い独立して単結合、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−、−CH=CH−、−CH=N−N=CH−又は−C≡C−が好ましく、単結合、−CH2CH2−、−(CH2)4−、−OCH2−又は−CH2O−がより好ましく、単結合、−CH2CH2−がさらに好ましい。さらに詳述すると、一般式(II)は、具体的な構造として以下の一般式(II-A)から一般式(II-P)からなる群で表される化合物が好ましい。M 21 , M 22 and M 23 are each independently a trans-1,4-cyclohexylene group (one CH 2 group present in this group or two non-adjacent CH 2 groups are oxygen atoms) Including a substituted group), a 1,4-phenylene group (including one or more CH groups present in this group substituted by a nitrogen atom), 3-fluoro-1, 4-phenylene group, 3,5-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene -2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is preferred, trans-1,4-cyclohexylene group, 1 , 4-phenylene group or 1,4-bicyclo [2.2.2] octylene group is more preferable, and trans-1,4-cyclohexylene group or 1,4-phenylene group is particularly preferable. preferable. o is preferably 0, 1 or 2, more preferably 0 or 1. L 21 and L 22 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— , -CH = CH -, - CH = N-N = CH- or -C≡C-, more preferably a single bond, -CH 2 CH 2 -, - (CH 2) 4 -, - OCH 2 - or -CH 2 O- is more preferable, and a single bond, -CH 2 CH 2 -is more preferable. More specifically, the general formula (II) is preferably a compound represented by the group consisting of the following general formula (II-A) to general formula (II-P) as a specific structure.
(式中、R23及びR24は、それぞれ独立的に炭素数1から10のアルキル基、炭素数1から10のアルコキシ基、炭素数2から10のアルケニル基又は炭素数3から10のアルケニルオキシ基を表す。)
R23及びR24は、それぞれ独立的に炭素数1から10のアルキル基、炭素数1から10のアルコキシ基又は炭素数2から10のアルケニル基がより好ましく、炭素数1から5のアルキル基又は炭素数1から10のアルコキシ基が更に好ましい。
一般式(II-A)から一般式(II-P)で表される化合物中、一般式(II-A)、一般式(II-B)、一般式(II-C)、一般式(II-E)、一般式(II-H)、 一般式(II-I)、一般式(II-I)、又は一般式(II-K)で表される化合物が好ましく、一般式(II-A)、一般式(II-C)、一般式(II-E)、 一般式(II-H)又は一般式(II-I)で表される化合物が更に好ましい。(Wherein R 23 and R 24 are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 3 to 10 carbon atoms) Represents a group.)
R 23 and R 24 are each independently preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or More preferred are alkoxy groups having 1 to 10 carbon atoms.
Among the compounds represented by general formula (II-A) to general formula (II-P), general formula (II-A), general formula (II-B), general formula (II-C), and general formula (II) -E), general formula (II-H), general formula (II-I), general formula (II-I), or a compound represented by general formula (II-K) is preferred, and general formula (II-A ), General formula (II-C), general formula (II-E), general formula (II-H) or general formula (II-I) is more preferred.
本願発明では一般式(II)で表される化合物を少なくとも1種を含有するが、1種〜10種含有することが好ましく、2種〜8種含有することが特に好ましく、一般式(II)で表される化合物の含有率の下限値は5質量%であることが好ましく、10質量%であることがより好ましく、20質量%であることが更に好ましく、30質量%であることが特に好ましく、上限値としては80質量%が好ましく、70質量%が更に好ましく、60質量%が更に好ましい。 In the present invention, it contains at least one compound represented by the general formula (II), preferably 1 to 10 types, more preferably 2 to 8 types, and particularly preferably the general formula (II). Is preferably 5% by mass, more preferably 10% by mass, still more preferably 20% by mass, and particularly preferably 30% by mass. The upper limit is preferably 80% by mass, more preferably 70% by mass, and still more preferably 60% by mass.
第三成分として使用する一般式(IIIa)、一般式(IIIb)及び一般式(IIIc) で表される化合物において、R31、R32及びR33はお互い独立して炭素原子数1から10のアルキル基又は炭素原子数2から10のアルケニル基、炭素数1〜15の直鎖状アルキル基又は炭素数2〜15のアルケニル基(これらの基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置換されているもの、またこれらの基中に存在する1個又は2個以上の水素原子はフッ素原子又は塩素原子に置換されているものも含む。)を表すことが好ましく、炭素数1〜10の直鎖状アルキル基、炭素数1〜10の直鎖状アルコキシ基又は炭素数2〜10アルケニル基を表すことがより好ましく、炭素数1〜8の直鎖状アルキル基又は炭素数1〜8のアルコキシ基を表すことが特に好ましい。
M31、M32、M33、M34、M35、M36、M37、及びM38はお互い独立して、トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置き換えられているものも含む。)、1,4-フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は窒素原子に置き換えられているものも含む)、1,4-シクロヘキセニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ピペリジン-1,4-ジイル基、ナフタレン-2,6-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基及びデカヒドロナフタレン-2,6-ジイル基で表す基(各々の基はそれぞれ水素原子がシアノ基、フッ素原子、トリフルオロメチル基、トリフルオロメトキシ基又は塩素原子で置換されているものも含む。)が好ましく、トランス-1,4-シクロへキシレン基、1,4-フェニレン基、3-フルオロ-1,4-フェニレン基又は3,5-ジフルオロ-1,4-フェニレン基を表すことがより好ましく、トランス-1,4-シクロへキシレン基又は1,4-フェニレン基を表すことが更に好ましく、トランス-1,4-シクロへキシレン基を表すことが特に好ましい。In the compounds represented by the general formula (IIIa), general formula (IIIb) and general formula (IIIc) used as the third component, R 31 , R 32 and R 33 are each independently of 1 to 10 carbon atoms. An alkyl group or an alkenyl group having 2 to 10 carbon atoms, a linear alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms (one methylene group present in these groups or adjacent thereto). Two or more methylene groups not substituted by —O— or —S—, and one or more hydrogen atoms present in these groups are substituted by fluorine atoms or chlorine atoms In particular, a linear alkyl group having 1 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms is more preferable. A linear alkyl group having 1 to 8 carbon atoms or 1 to 8 carbon atoms It is particularly preferred to represent an alkoxy group.
M 31 , M 32 , M 33 , M 34 , M 35 , M 36 , M 37 , and M 38 are each independently a trans-1,4-cyclohexylene group (one of the groups present in this group). A methylene group or two or more methylene groups not adjacent to each other include those in which -O- or -S- is substituted.), 1,4-phenylene group (one -CH present in this group) = Or two or more non-adjacent —CH═ include those substituted with nitrogen atoms), 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine- Groups represented by 1,4-diyl group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group (each Groups also include those in which each hydrogen atom is replaced by a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom And preferably represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 3-fluoro-1,4-phenylene group, or a 3,5-difluoro-1,4-phenylene group. Preferably, it represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group, more preferably a trans-1,4-cyclohexylene group.
L31、L32、L33、L34、L35、L36、L37及びL38はお互い独立して単結合、−OCO−、−COO−、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−又は−C≡C−を表すことが好ましく、単結合、−CH2CH2−、−(CH2)4−又は−C≡C−を表すことがより好ましく、単結合又は−CH2CH2−が特に好ましい。X31、X32、X33、X34、X35、X36、及びX37はお互い独立して水素原子又はフッ素原子をし、Y31、Y32、及びY33はお互い独立して水素原子、フッ素原子、塩素原子、シアノ基、チオシアナト基、トリフルオロメトキシ基、トリフルオロメチル基、2,2,2-トリフルオロエチル基、ジフルオロメトキシ基又は炭素原子数1〜12のアルキル基を表すことが好ましく、水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメトキシ基、トリフルオロメチル基、2,2,2-トリフルオロエチル基又は炭素原子数1〜12のアルキル基を表すことが好ましく、フッ素原子を表すことが特に好ましい。p、q、r、s、及びtはお互い独立して、0、1又は2を表すが、q+r及びs+tは2以下を表す。L 31 , L 32 , L 33 , L 34 , L 35 , L 36 , L 37 and L 38 are each independently a single bond, —OCO—, —COO—, —CH 2 CH 2 —, — (CH 2 ) 4 -, - OCH 2 - , - CH 2 O -, - OCF 2 -, - it is preferable to represent a CF 2 O-or -C≡C-, a single bond, -CH 2 CH 2 -, - (CH 2 ) It is more preferable to represent 4 — or —C≡C—, and a single bond or —CH 2 CH 2 — is particularly preferable. X 31 , X 32 , X 33 , X 34 , X 35 , X 36 , and X 37 are each independently a hydrogen atom or a fluorine atom, and Y 31 , Y 32 , and Y 33 are each independently a hydrogen atom. Represents a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a difluoromethoxy group, or an alkyl group having 1 to 12 carbon atoms. And preferably represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, or an alkyl group having 1 to 12 carbon atoms. And particularly preferably represents a fluorine atom. p, q, r, s, and t each independently represent 0, 1 or 2, but q + r and s + t represent 2 or less.
具体的には以下の一般式(IIIa-1)で示される構造を表すことが好ましい。 Specifically, it is preferable to represent a structure represented by the following general formula (IIIa-1).
(式中、R34は炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表し、L39及びL40はそれぞれ独立して単結合、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−又は−C≡C−を表し、M39は1,4-フェニレン基又はトランス-1,4-シクロヘキシレン基を表し、X32は水素原子又はフッ素原子を表し、p1は0又は1を表し、Y34はシアノ基、フッ素原子、塩素原子、トリフルオロメチル基、フルオロメトキシ基、ジフルオロメトキシ基又はトリフルオロメトキシ基を表す。)
さらに具体的には以下の一般式(IIIa-2a)〜一般式(IIIa-4d)(Wherein R 34 represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, and L 39 and L 40 are each independently a single atom. bond, -CH 2 CH 2 -, - (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O- or represents -C≡C-, M 39 is 1,4-phenylene group or trans-1,4-cyclohexylene group, X 32 represents a hydrogen atom or a fluorine atom, p 1 represents 0 or 1, Y 34 represents a cyano group, a fluorine atom, a chlorine atom Represents a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group.)
More specifically, the following general formula (IIIa-2a) to general formula (IIIa-4d)
(式中、R34は炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表し、X31及びX32はそれぞれ独立して水素原子又はフッ素原子を表し、Y34はシアノ基、フッ素原子、塩素原子、トリフルオロメチル基、フルオロメトキシ基、ジフルオロメトキシ基又はトリフルオロメトキシ基を表す。)で表される構造が好ましく、(Wherein R 34 represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and X 31 and X 32 are each independently hydrogen. represents an atom or a fluorine atom, Y 34 is a cyano group, a fluorine atom, a chlorine atom, trifluoromethyl group, trifluoromethoxy group, a structure represented by.) representing a difluoromethoxy group or a trifluoromethoxy group are preferred,
(式中、R34は炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表し、Y34はシアノ基、フッ素原子、塩素原子、トリフルオロメチル基、フルオロメトキシ基、ジフルオロメトキシ基又はトリフルオロメトキシ基を表す。)で表される構造を表すことも好ましい。(In the formula, R 34 represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and Y 34 represents a cyano group, a fluorine atom, or a chlorine atom. , A trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group).
一般式(IIIb)は具体的な構造として以下の一般式 General formula (IIIb) has the following general formula as a specific structure:
(式中、R35は炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表し、Y35はシアノ基、フッ素原子、塩素原子、トリフルオロメチル基、フルオロメトキシ基、ジフルオロメトキシ基又はトリフルオロメトキシ基を表す。)で表される構造が好ましく、
一般式(IIIc)は具体的な構造として以下の一般式(In the formula, R 35 represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and Y 35 represents a cyano group, a fluorine atom, or a chlorine atom. Represents a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group).
General formula (IIIc) has the following general formula as a specific structure:
(式中、R36は炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表し、Y36はシアノ基、フッ素原子、塩素原子、トリフルオロメチル基、フルオロメトキシ基、ジフルオロメトキシ基又はトリフルオロメトキシ基を表す。)で表される構造が好ましい。
一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)で表される化合物からなる群から選ばれる化合物を少なくとも1種を含有するが、1種〜10種含有することが好ましく、2種〜8種含有することが特に好ましく、一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)で表される化合物からなる群の含有率の下限値は5質量%であることが好ましく、10質量%であることがより好ましく、20質量%であることが好ましく、上限値は80質量%が好ましく、70質量%が好ましく、60質量%が好ましく、50質量%が更に好ましい。(In the formula, R 36 represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and Y 36 represents a cyano group, a fluorine atom, or a chlorine atom. , Represents a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group).
It contains at least one compound selected from the group consisting of compounds represented by general formula (IIIa), general formula (IIIb) and general formula (IIIc), preferably 1 to 10 types. It is particularly preferable to contain 8 to 8 species, and the lower limit of the content of the group consisting of the compounds represented by the general formula (IIIa), general formula (IIIb) and general formula (IIIc) is 5% by mass. Preferably, it is more preferably 10% by mass, preferably 20% by mass, and the upper limit is preferably 80% by mass, preferably 70% by mass, preferably 60% by mass, and further preferably 50% by mass.
また、一般式(IVa)、一般式(IVb)及び一般式(IVc)で表される化合物において、R41、R42、R43、R44、R45及びR46はお互い独立して炭素原子数1から10のアルキル基又は炭素原子数2から10のアルケニル基、炭素数1〜15の直鎖状アルキル基又は炭素数2〜15のアルケニル基(これらの基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置換されているもの、またこれらの基中に存在する1個又は2個以上の水素原子はフッ素原子又は塩素原子に置換されているものも含む。)を表すことが好ましく、炭素数1〜10の直鎖状アルキル基、炭素数1〜10の直鎖状アルコキシ基又は炭素数2〜10アルケニル基を表すことがより好ましく、炭素数1〜8の直鎖状アルキル基又は炭素数1〜8のアルコキシ基を表すことが特に好ましい。M41、M42、M43、M44、M45、M46、M47、M48及びM49はお互い独立して、トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置き換えられているものも含む。)、1,4-フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は窒素原子に置き換えられているものも含む)、1,4-シクロヘキセニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ピペリジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基及びデカヒドロナフタレン-2,6-ジイル基で表す基(各々の基に含まれる水素原子がそれぞれシアノ基、フッ素原子、トリフルオロメチル基、トリフルオロメトキシ基又は塩素原子で置換されているものも含む。)が好ましく、トランス-1,4-シクロへキシレン基、1,4-フェニレン基、3-フルオロ-1,4-フェニレン基又は2,3-ジフルオロ-1,4-フェニレン基を表すことがより好ましく、トランス-1,4-シクロへキシレン基又は1,4-フェニレン基を表すことが更に好ましく、トランス-1,4-シクロへキシレン基を表すことが特に好ましい。L41、L42、L43、L44、L45、L46、L47、L48及びL49はお互い独立して単結合、−CH2CH2−、−(CH2)4−、−OCO−、−COO−、−OCH2−、−CH2O−、−OCF2−、−CF2O−又は−C≡C−を表すことが好ましく、単結合、−CH2CH2−、−OCH2−、又は−CH2O−を表すことがより好ましい。X41、X42、X43、X44、X45、X46、及びX47はお互い独立して水素原子又はフッ素原子を表し、Gはメチレン基又は−O−を表し、u、v、w、x、y及びzはお互い独立して、0、1又は2を表すが、u+v、w+x及びy+zは2以下で表す。In the compounds represented by general formula (IVa), general formula (IVb) and general formula (IVc), R 41 , R 42 , R 43 , R 44 , R 45 and R 46 are each independently a carbon atom. An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a linear alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms (one methylene present in these groups) A group or two or more methylene groups not adjacent to each other are substituted by —O— or —S—, and one or more hydrogen atoms present in these groups are fluorine atoms or chlorine atoms It is also preferable to represent a linear alkyl group having 1 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. Is more preferable, a linear alkyl group having 1 to 8 carbon atoms or an aryl group having 1 to 8 carbon atoms. And particularly preferably a Kokishi group. M 41 , M 42 , M 43 , M 44 , M 45 , M 46 , M 47 , M 48 and M 49 are each independently a trans-1,4-cyclohexylene group (1 present in this group). Methylene groups or two or more methylene groups not adjacent to each other include those in which -O- or -S- is substituted.), 1,4-phenylene group (one in this group) -CH = or two or more non-adjacent -CH = are substituted with nitrogen atoms), 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, Groups represented by piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group ( A hydrogen atom contained in each group is substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, or a chlorine atom, respectively. And a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 3-fluoro-1,4-phenylene group or a 2,3-difluoro-1,4-phenylene group. More preferably, it represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group, more preferably a trans-1,4-cyclohexylene group. L 41 , L 42 , L 43 , L 44 , L 45 , L 46 , L 47 , L 48 and L 49 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, — OCO -, - COO -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - it is preferable to represent a CF 2 O-or -C≡C-, a single bond, -CH 2 CH 2 -, It is more preferable to represent —OCH 2 — or —CH 2 O—. X 41 , X 42 , X 43 , X 44 , X 45 , X 46 , and X 47 each independently represent a hydrogen atom or a fluorine atom, G represents a methylene group or —O—, and u, v, w , X, y and z each independently represent 0, 1 or 2, but u + v, w + x and y + z are each represented by 2 or less.
一般式(IVa)で表される化合物において、具体的には以下の一般式(IVa-1)で示される構造を表すことが好ましい。 In the compound represented by the general formula (IVa), it is preferable to specifically represent the structure represented by the following general formula (IVa-1).
(式中、R47 及びR48はお互い独立して炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表し、L50、L51及びL52はそれぞれ独立して単結合、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−又は−C≡C−を表し、M50は1,4-フェニレン基又はトランス-1,4-シクロヘキシレン基を表し、u1及びv1は、それぞれ独立して0又は1を表す。)
さらに具体的には以下の一般式(IVa-2a)〜一般式(IVa-3i)(In the formula, R 47 and R 48 independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, L 50 , L 51 and L 52 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— or — C≡C—, M 50 represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and u 1 and v 1 each independently represents 0 or 1.)
More specifically, the following general formula (IVa-2a) to general formula (IVa-3i)
(式中、R47及びR48は、それぞれ独立して炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表す。)で表される構造が好ましく、R47及びR48がそれぞれ独立して炭素原子数1〜8のアルキル基又は炭素原子数1〜8のアルコキシル基で表される構造が更に好ましい。(Wherein R 47 and R 48 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms). A structure in which R 47 and R 48 are each independently an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms is more preferable.
一般式(IVb)で表される化合物において、具体的には以下の一般式(IVb-1)で示される構造を表すことが好ましい。 In the compound represented by the general formula (IVb), specifically, a structure represented by the following general formula (IVb-1) is preferably represented.
(式中、R49 及びR50はお互い独立して炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表し、L53、L54及びL55はそれぞれ独立して単結合、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−又は−C≡C−を表し、M51、M52及びM53は1,4-フェニレン基又はトランス-1,4-シクロヘキシレン基を表し、w1及びx1は、独立して0、1又は2を表すが、w1+x1は2以下を表す。)
さらに具体的には以下の一般式(IVb-2a)〜(IVb-3l)(In the formula, R 49 and R 50 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, L 53 , L 54 and L 55 each independently represent a single bond, -CH 2 CH 2 -, - (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O- or - C≡C—, M 51 , M 52 and M 53 represent a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and w 1 and x 1 independently represent 0, 1 or 2. W1 + x1 represents 2 or less.)
More specifically, the following general formulas (IVb-2a) to (IVb-3l)
(式中、R49及びR50は、それぞれ独立して炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表す。)で表される構造が好ましい。(Wherein R 49 and R 50 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms). The structure is preferred.
一般式(IVc)で表される化合物において、具体的には以下の一般式(IVc-1a)及び一般式(IVc-1b)で示される構造を表すことが好ましい。 In the compound represented by the general formula (IVc), specifically, it is preferable to represent a structure represented by the following general formula (IVc-1a) and general formula (IVc-1b).
(式中、R51 及びR52はお互い独立して炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表し、L56、L57及びL58はそれぞれ独立して単結合、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−又は−C≡C−を表し、M54、M55及びM56は1,4-フェニレン基又はトランス-1,4-シクロヘキシレン基を表し、y1及びz1は、独立して0、1又は2を表すが、y1+z1は2以下を表す。)
さらに具体的には以下の一般式(IVc-2a)〜(IVc-2g)(In the formula, R 51 and R 52 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, L 56 , L 57 and L 58 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— or — C≡C—, M 54 , M 55 and M 56 represent 1,4-phenylene group or trans-1,4-cyclohexylene group, and y 1 and z 1 independently represent 0, 1 or 2. However, y1 + z1 represents 2 or less.)
More specifically, the following general formulas (IVc-2a) to (IVc-2g)
(式中、R51 及びR52はお互い独立して炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基又は炭素原子数2〜8のアルケニル基を表す。)
第三成分として使用する一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)で表される化合物からなる群から選ばれる化合物、又は一般式(IVa)、一般式(IVb)及び一般式(IVc)で表される化合物からなる群から選ばれる化合物を少なくとも1種を含有するが、2種〜10種含有することが好ましく、2種〜8種含有することが特に好ましく、含有率の下限値が5質量%であることが好ましく、10質量%であることがより好ましく、20質量%であることがより好ましく、上限値が80質量%であることが好ましく、70質量%であることが好ましく、60質量%であることが好ましく、50質量%であることが好ましい。(In the formula, R 51 and R 52 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms.)
A compound selected from the group consisting of compounds represented by general formula (IIIa), general formula (IIIb) and general formula (IIIc) used as the third component, or general formula (IVa), general formula (IVb) and general It contains at least one compound selected from the group consisting of the compounds represented by formula (IVc), but preferably contains 2 to 10 types, particularly preferably contains 2 to 8 types, and the content rate The lower limit is preferably 5% by mass, more preferably 10% by mass, more preferably 20% by mass, and the upper limit is preferably 80% by mass, and is 70% by mass. It is preferably 60% by mass, and preferably 50% by mass.
本願発明の液晶組成物において、Δnは0.08〜0.25の範囲であることが好ましい。 In the liquid crystal composition of the present invention, Δn is preferably in the range of 0.08 to 0.25.
本願発明の液晶組成物において、Δεは液晶表示素子の表示モードによって、正、又は負のΔεを有するものを用いることができる。MVAモードの液晶表示素子においては、負のΔεを有する液晶組成物を使用する。その場合のΔεは、−1以下が好ましく、−2以下がより好ましい。 In the liquid crystal composition of the present invention, Δε having a positive or negative Δε can be used depending on the display mode of the liquid crystal display element. In the MVA mode liquid crystal display element, a liquid crystal composition having a negative Δε is used. In that case, Δε is preferably −1 or less, and more preferably −2 or less.
本願発明の液晶組成物は、広い液晶相温度範囲(液晶相下限温度と液晶相上限温度の差の絶対値)を有するが、液晶相温度範囲が100℃以上であることが好ましく、120℃以上がより好ましい。また、液晶相上限温度は70℃以上であることが好ましく、80℃以上がより好ましい。さらに、液晶相下限温度は−20℃以下であることが好ましく、−30℃以下がより好ましい。 The liquid crystal composition of the present invention has a wide liquid crystal phase temperature range (the absolute value of the difference between the liquid crystal phase lower limit temperature and the liquid crystal phase upper limit temperature), but the liquid crystal phase temperature range is preferably 100 ° C. or higher, preferably 120 ° C. or higher. Is more preferable. The upper limit temperature of the liquid crystal phase is preferably 70 ° C. or higher, and more preferably 80 ° C. or higher. Furthermore, the liquid crystal phase lower limit temperature is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.
本願発明の液晶組成物は、上記の化合物以外に、通常のネマチック液晶、スメクチック液晶、コレステリック液晶などを含有していてもよい。 The liquid crystal composition of the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal and the like in addition to the above compounds.
本願発明の重合性化合物を含有する液晶組成物は、重合開始剤が存在しない場合でも重合は進行するが、重合を促進するために重合開始剤を含有していてもよい。重合開始剤としては、ベンゾインエーテル類、ベンゾフェノン類、アセトフェノン類、ベンジルケタール類、アシルフォスフィンオキサイド類等が挙げられる。 The liquid crystal composition containing the polymerizable compound of the present invention is polymerized even when no polymerization initiator is present, but may contain a polymerization initiator in order to accelerate the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.
本願発明の液晶組成物には、その保存安定性を向上させるために、安定剤を添加することもできる。使用できる安定剤としては、例えば、ヒドロキノン類、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、β−ナフチルアミン類、β−ナフトール類、ニトロソ化合物等が挙げられる。安定剤を使用する場合の添加量は、液晶組成物に対して0.005〜1質量%の範囲が好ましく、0.02〜0.5質量%がさらに好ましく、0.03〜0.1質量%が特に好ましい。 In order to improve the storage stability of the liquid crystal composition of the present invention, a stabilizer may be added. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the amount added is preferably 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0.1% by mass with respect to the liquid crystal composition. % Is particularly preferred.
本願発明の液晶組成物は、液晶組成物中の重合性化合物が重合することにより液晶配向能が付与され、液晶組成物の複屈折を利用して光の透過光量を制御する液晶表示素子に使用される。液晶表示素子として、AM-LCD(アクティブマトリックス液晶表示素子)、TN(ネマチック液晶表示素子)、STN-LCD(超ねじれネマチック液晶表示素子)、OCB-LCD及びIPS-LCD(インプレーンスイッチング液晶表示素子)に有用であるが、AM-LCDに特に有用であり、透過型あるいは反射型の液晶表示素子に用いることができる。 The liquid crystal composition of the present invention is used for a liquid crystal display element that is provided with liquid crystal alignment ability by polymerization of a polymerizable compound in the liquid crystal composition and controls the amount of light transmitted using the birefringence of the liquid crystal composition. Is done. As liquid crystal display elements, AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD and IPS-LCD (in-plane switching liquid crystal display element) However, it is particularly useful for AM-LCDs, and can be used for transmissive or reflective liquid crystal display elements.
液晶表示素子に使用される液晶セルの2枚の基板はガラス、プラスチックの如き柔軟性をもつ透明な材料を用いることができ、一方はシリコン等の不透明な材料でも良い。透明電極層を有する透明基板は、例えば、ガラス板等の透明基板上にインジウムスズオキシド(ITO)をスパッタリングすることにより得ることができる。 The two substrates of the liquid crystal cell used in the liquid crystal display element can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.
カラーフィルターは、例えば、顔料分散法、印刷法、電着法、又は、染色法等によって作成することができる。顔料分散法によるカラーフィルターの作成方法を一例に説明すると、カラーフィルター用の硬化性着色組成物を、該透明基板上に塗布し、パターニング処理を施し、そして加熱又は光照射により硬化させる。この工程を、赤、緑、青の3色についてそれぞれ行うことで、カラーフィルター用の画素部を作成することができる。その他、該基板上に、TFT、薄膜ダイオード、金属絶縁体金属比抵抗素子等の能動素子を設けた画素電極を設置してもよい。 The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.
前記基板を、透明電極層が内側となるように対向させる。その際、スペーサーを介して、基板の間隔を調整してもよい。このときは、得られる調光層の厚さが1〜100μmとなるように調整するのが好ましい。1.5から10μmが更に好ましく、偏光板を使用する場合は、コントラストが最大になるように液晶の屈折率異方性Δnとセル厚dとの積を調整することが好ましい。又、二枚の偏光板がある場合は、各偏光板の偏光軸を調整して視野角やコントラトが良好になるように調整することもできる。更に、視野角を広げるための位相差フィルムも使用することもできる。スペーサーとしては、例えば、ガラス粒子、プラスチック粒子、アルミナ粒子、フォトレジスト材料等が挙げられる。その後、エポキシ系熱硬化性組成物等のシール剤を、液晶注入口を設けた形で該基板にスクリーン印刷し、該基板同士を貼り合わせ、加熱しシール剤を熱硬化させる。 The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. In that case, you may adjust the space | interval of a board | substrate through a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be set to 1-100 micrometers. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.
2枚の基板間に高分子安定化液晶組成物を狭持させるに方法は、通常の真空注入法、又はODF法などを用いることができる。 As a method for sandwiching the polymer-stabilized liquid crystal composition between the two substrates, a normal vacuum injection method, an ODF method, or the like can be used.
重合性化合物を重合させる方法としては、迅速な重合の進行が望ましいので、紫外線又は電子線等の活性エネルギー線を照射することによって重合させる方法が好ましい。紫外線を使用する場合、偏光光源を用いても良いし、非偏光光源を用いても良い。また、液晶組成物を2枚の基板間に挟持させて状態で重合を行う場合には、少なくとも照射面側の基板は活性エネルギー線に対して適当な透明性が与えられていなければならない。また、光照射時にマスクを用いて特定の部分のみを重合させた後、電場や磁場又は温度等の条件を変化させることにより、未重合部分の配向状態を変化させて、さらに活性エネルギー線を照射して重合させるという手段を用いても良い。特に紫外線露光する際には、液晶組成物に交流を印加しながら紫外線露光することが好ましい。印加する交流は、周波数500Hzから10kHzの交流が好ましく、周波数1kHzから10kHzがより好ましい。 As a method for polymerizing a polymerizable compound, since rapid progress of polymerization is desirable, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating current to the liquid crystal composition. The alternating current to be applied is preferably an alternating current having a frequency of 500 Hz to 10 kHz, and more preferably a frequency of 1 kHz to 10 kHz.
照射時の温度は、本願発明の液晶組成物の液晶状態が保持される温度範囲内であることが好ましい。室温に近い温度、即ち、典型的には15〜35℃での温度で重合させることが好ましい。紫外線を発生させるランプとしては、メタルハライドランプ、高圧水銀ランプ、超高圧水銀ランプ等を用いることができる。また、照射する紫外線の波長としては、液晶組成物の吸収波長域でない波長領域の紫外線を照射することが好ましく、必要に応じて、紫外線をカットして使用することが好ましい。照射する紫外線の強度は、0.1mW/cm2〜50W/cm2が好ましく、2mW/cm2〜20W/cm2がより好ましい。照射する紫外線のエネルギー量は、適宜調整することができるが、10から10000mJ/cm2が好ましく、100から7000mJ/cm2がより好ましい。紫外線を照射する際に、強度を変化させても良い。紫外線を照射する時間は照射する紫外線強度により適宜選択されるが、10から600秒が好ましい。The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-rays to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed. Intensity of ultraviolet irradiation is preferably from 0.1mW / cm 2 ~50W / cm 2 , 2mW / cm 2 ~20W / cm 2 is more preferable. Energy of ultraviolet light irradiation, can be appropriately adjusted, is preferably 10000 mJ / cm 2 to 10, more preferably 7000mJ / cm 2 to 100. When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiation with ultraviolet rays is appropriately selected depending on the intensity of ultraviolet rays to be irradiated, but is preferably 10 to 600 seconds.
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.
液晶組成物の物性として、以下のように表す。
TN-I :ネマチック相−等方性液体相転移温度(℃)を液晶相上限温度
Δε :誘電率異方性
Δn :屈折率異方性
Vth :周波数1KHzの矩形波を印加した時の透過率が10%変化する印加電圧(しきい値電圧)
(UV硬化後のモノマー残存量の測定方法)
液晶セルに液晶組成物を注入後、UVを照射し重合性化合物を重合させる。その後、液晶セルを分解し、液晶材料、重合物、未重合の重合性化合物を含む溶出成分のアセトニトリル溶液を得る。これを高速液体クロマトグラフィー(カラム:、展開溶媒:アセトニトリル)により、各成分のピーク面積を測定する。指標とする液晶材料のピーク面積と未重合の重合性化合物のピーク面積比から、残存する重合性化合物の量を決定した。この値と当初添加した重合性化合物の量からモノマー残存量を決定した。なお、重合性化合物の残存量の検出限界は1000ppmであった。
(実施例1)
一般式(II)から選ばれる化合物、一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)から選ばれる化合物又は、一般式(IVa)、一般式(IVb)及び一般式(IVc)から選ばれる化合物を含有した液晶組成物LC−1を調製した。構成する化合物及び含有する比率は以下の通りである。The physical properties of the liquid crystal composition are expressed as follows.
T NI : Nematic phase-isotropic liquid phase transition temperature (° C), liquid crystal phase upper limit temperature Δε: Dielectric anisotropy Δn: Refractive index anisotropy
Vth: Applied voltage (threshold voltage) at which the transmittance changes by 10% when a rectangular wave with a frequency of 1 KHz is applied
(Measurement method of residual amount of monomer after UV curing)
After injecting the liquid crystal composition into the liquid crystal cell, UV is irradiated to polymerize the polymerizable compound. Thereafter, the liquid crystal cell is disassembled to obtain an acetonitrile solution of an elution component containing a liquid crystal material, a polymer, and an unpolymerized polymerizable compound. The peak area of each component is measured by high performance liquid chromatography (column :, developing solvent: acetonitrile). The amount of the remaining polymerizable compound was determined from the peak area ratio of the liquid crystal material as an index and the peak area ratio of the unpolymerized polymerizable compound. The residual monomer amount was determined from this value and the amount of the polymerizable compound initially added. The detection limit of the remaining amount of the polymerizable compound was 1000 ppm.
Example 1
Compound selected from general formula (II), compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) A liquid crystal composition LC-1 containing a compound selected from: The constituent compounds and the ratios contained are as follows.
上記液晶組成物LC−1の物性を表1に示す。 Table 1 shows the physical properties of the liquid crystal composition LC-1.
液晶組成物LC−1 99.7%に対して、一般式(I-1)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−1を調製した。CLC−1の物性は上記のLC−1の物性とほとんど違いはなかった。CLC−1をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角(クリスタルローテーション法)を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前後のプレチルト角及び素子の電気光学特性を表2に示す。A polymerizable liquid crystal composition CLC-1 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-1) to 99.7% of the liquid crystal composition LC-1 and uniformly dissolving it. . The physical properties of CLC-1 were almost the same as the physical properties of LC-1. CLC-1 was injected by a vacuum injection method into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle (crystal rotation method) of this cell, the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp through a filter that cuts ultraviolet light of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. did. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. Table 2 shows the pretilt angle of the element before and after UV irradiation and the electro-optical characteristics of the element.
上記のプレチルト角の結果から、重合性化合物が重合することにより、液晶分子にプレチルトが付与された垂直配向性液晶表示素子を得ることがわかった。
また、液体クロマトグラフ分析により、素子中に含有する一般式(I-1)で示される化合物の含有量を分析したが、検出されなかった。これにより、一般式(I-1)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(比較例1)
液晶組成物LC−1 99.7%に対して、一般式(A)From the result of the above-mentioned pretilt angle, it was found that a vertical alignment liquid crystal display element in which a pretilt was imparted to liquid crystal molecules was obtained by polymerization of the polymerizable compound.
Further, the content of the compound represented by the general formula (I-1) contained in the device was analyzed by liquid chromatographic analysis, but it was not detected. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-1) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Comparative Example 1)
With respect to 99.7% of liquid crystal composition LC-1, the general formula (A)
で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−Aを調製した。CLC−Aをセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.6度であったのに対して、照射後のプレチルト角は89.5度とプレチルトが付与されていなかった。液体クロマトグラフ分析により、素子中に含有する一般式(A)で示される化合物の含有量を分析した結果、紫外線照射前と含有量に変化はなく、重合性化合物(A)の重合は進行していなかった。
(実施例2)
液晶組成物LC−1 99.7%に対して、一般式(I-2)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−2を調製した。CLC−2をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.6度であったのに対して、照射後のプレチルト角は87.4度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-2)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-2)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例3)
液晶組成物LC−1 99.7%に対して、一般式(I-20)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−3を調製した。CLC−3をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.5度であったのに対して、照射後のプレチルト角は87.7度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-20)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-20)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例4)
液晶組成物LC−1 99.7%に対して、一般式(I-36)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−7を調製した。CLC−7をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.5度であったのに対して、照射後のプレチルト角は87.1度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-36)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-36)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例5)
液晶組成物LC−1 99.7%に対して、一般式(I-37)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−8を調製した。CLC−8をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.7度であったのに対して、照射後のプレチルト角は87.3度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-37)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-37)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例6)
液晶組成物LC−1 99.7%に対して、一般式(I-38)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−9を調製した。CLC−9をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.6度であったのに対して、照射後のプレチルト角は87.7度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-38)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-38)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例7)
液晶組成物LC−1 99.7%に対して、一般式(I-39)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−10を調製した。CLC−10をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.7度であったのに対して、照射後のプレチルト角は87.1度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-39)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-39)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例8)
一般式(II)から選ばれる化合物、一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)から選ばれる化合物又は、一般式(IVa)、一般式(IVb)及び一般式(IVc)から選ばれる化合物を含有した実例として以下のような構成成分の液晶組成物LC−2を調製した。A polymerizable liquid crystal composition CLC-A was prepared by adding 0.3% of the polymerizable compound represented by the formula (II) and dissolving it uniformly. CLC-A was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.6 degrees, whereas the pretilt angle after the irradiation was 89.5 degrees and no pretilt was imparted. As a result of analyzing the content of the compound represented by the general formula (A) contained in the element by liquid chromatographic analysis, there is no change in the content before ultraviolet irradiation, and the polymerization of the polymerizable compound (A) proceeds. It wasn't.
(Example 2)
A polymerizable liquid crystal composition CLC-2 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-2) to 99.7% of the liquid crystal composition LC-1 and uniformly dissolving it. . CLC-2 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.6 degrees, whereas the pretilt angle after the irradiation was 87.4 degrees, and a pretilt was given. The content of the compound represented by the general formula (I-2) contained in the device was analyzed by liquid chromatographic analysis, but was below the detection limit. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-2) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Example 3)
A polymerizable liquid crystal composition CLC-3 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-20) to 99.7% of the liquid crystal composition LC-1 and uniformly dissolving it. . CLC-3 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.5 degrees, whereas the pretilt angle after the irradiation was 87.7 degrees, and a pretilt was imparted. The content of the compound represented by the general formula (I-20) contained in the device was analyzed by liquid chromatographic analysis, but was below the detection limit. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-20) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
Example 4
A polymerizable liquid crystal composition CLC-7 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-36) to 99.7% of the liquid crystal composition LC-1 and uniformly dissolving it. . CLC-7 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.5 degrees, whereas the pretilt angle after the irradiation was 87.1 degrees, and a pretilt was imparted. The content of the compound represented by the general formula (I-36) contained in the device was analyzed by liquid chromatographic analysis, but was below the detection limit. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-36) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Example 5)
A polymerizable liquid crystal composition CLC-8 was prepared by uniformly adding 0.3% of the polymerizable compound represented by the general formula (I-37) to 99.7% of the liquid crystal composition LC-1 and dissolving it uniformly. . CLC-8 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.7 degrees, whereas the pretilt angle after the irradiation was 87.3 degrees, and a pretilt was given. The content of the compound represented by the general formula (I-37) contained in the element was analyzed by liquid chromatographic analysis, but was below the detection limit. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-37) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Example 6)
A polymerizable liquid crystal composition CLC-9 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-38) to 99.7% of the liquid crystal composition LC-1 and uniformly dissolving it. . CLC-9 was injected into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm by a vacuum injection method. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.6 degrees, whereas the pretilt angle after the irradiation was 87.7 degrees, and a pretilt was given. The content of the compound represented by the general formula (I-38) contained in the device was analyzed by liquid chromatographic analysis, but was below the detection limit. As a result, it was confirmed that the polymerizable compound represented by the general formula (I-38) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Example 7)
A polymerizable liquid crystal composition CLC-10 was prepared by uniformly adding 0.3% of the polymerizable compound represented by the general formula (I-39) to 99.7% of the liquid crystal composition LC-1 and dissolving it uniformly. . CLC-10 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.7 degrees, whereas the pretilt angle after the irradiation was 87.1 degrees, and a pretilt was given. The content of the compound represented by the general formula (I-39) contained in the device was analyzed by liquid chromatographic analysis, but was below the detection limit. As a result, it was confirmed that the polymerizable compound represented by the general formula (I-39) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Example 8)
Compound selected from general formula (II), compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) As an example containing a compound selected from the following, a liquid crystal composition LC-2 having the following components was prepared.
上記液晶組成物LC−2の物性を表3に示す。 Table 3 shows the physical properties of the liquid crystal composition LC-2.
液晶組成物LC−2 99.7%に対して、一般式(I-1)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−4を調製した。CLC−4をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.6度であったのに対して、照射後のプレチルト角は87.4度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-1)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-1)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例9)
一般式(II)から選ばれる化合物、一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)から選ばれる化合物又は、一般式(IVa)、一般式(IVb)及び一般式(IVc)から選ばれる化合物を含有した実例として以下のような構成成分の液晶組成物LC−3を調製した。A polymerizable liquid crystal composition CLC-4 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-1) to 99.7% of the liquid crystal composition LC-2 and uniformly dissolving the compound. . CLC-4 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.6 degrees, whereas the pretilt angle after the irradiation was 87.4 degrees, and a pretilt was given. The content of the compound represented by the general formula (I-1) contained in the device was analyzed by liquid chromatographic analysis, but was below the detection limit. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-1) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
Example 9
Compound selected from general formula (II), compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) As an example containing a compound selected from the following, a liquid crystal composition LC-3 having the following components was prepared.
上記液晶組成物LC−3の物性を表4に示す。 Table 4 shows the physical properties of the liquid crystal composition LC-3.
液晶組成物LC−3 99.7%に対して、一般式(I-1)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−5を調製した。CLC−5をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.5度であったのに対して、照射後のプレチルト角は87.1度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-1)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-1)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例10)
一般式(II)から選ばれる化合物、一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)から選ばれる化合物又は、一般式(IVa)、一般式(IVb)及び一般式(IVc)から選ばれる化合物を含有した実例として以下のような構成成分の液晶組成物LC−4を調製した。A polymerizable liquid crystal composition CLC-5 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-1) to 99.7% of the liquid crystal composition LC-3 and uniformly dissolving the compound. . CLC-5 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.5 degrees, whereas the pretilt angle after the irradiation was 87.1 degrees, and a pretilt was imparted. The content of the compound represented by the general formula (I-1) contained in the device was analyzed by liquid chromatographic analysis, but was below the detection limit. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-1) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Example 10)
Compound selected from general formula (II), compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) As an example containing a compound selected from the following, a liquid crystal composition LC-4 having the following components was prepared.
上記液晶組成物LC−4の物性を表5に示す。 Table 5 shows the physical properties of the liquid crystal composition LC-4.
液晶組成物LC−4 99.7%に対して、一般式(I-1)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−6を調製した。CLC−6をセルギャップ3.5μmでパラレル配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、0.2度であったのに対して、照射後のプレチルト角は3.1度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-1)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-1)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例11)
一般式(II)から選ばれる化合物、一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)から選ばれる化合物又は、一般式(IVa)、一般式(IVb)及び一般式(IVc)から選ばれる化合物を含有した実例として以下のような構成成分の液晶組成物LC−5を調製した。A polymerizable liquid crystal composition CLC-6 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-1) to 99.7% of the liquid crystal composition LC-4 and uniformly dissolving it. . CLC-6 was injected by a vacuum injection method into a cell with ITO coated with a polyimide alignment film that induces parallel alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 0.2 degrees, whereas the pretilt angle after the irradiation was 3.1 degrees, and a pretilt was given. The content of the compound represented by the general formula (I-1) contained in the device was analyzed by liquid chromatographic analysis, but was below the detection limit. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-1) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Example 11)
Compound selected from general formula (II), compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) As an example containing a compound selected from the following, a liquid crystal composition LC-5 having the following components was prepared.
上記液晶組成物LC−5の物性を表6に示す。 Table 6 shows the physical properties of the liquid crystal composition LC-5.
液晶組成物LC−5 99.7%に対して、一般式(I-2)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−11を調製した。CLC−11をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.6度であったのに対して、照射後のプレチルト角は87.0度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-2)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-2)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例12)
一般式(II)から選ばれる化合物、一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)から選ばれる化合物又は、一般式(IVa)、一般式(IVb)及び一般式(IVc)から選ばれる化合物を含有した実例として以下のような構成成分の液晶組成物LC−6を調製した。A polymerizable liquid crystal composition CLC-11 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-2) to 99.7% of the liquid crystal composition LC-5 and uniformly dissolving it. . CLC-11 was injected by a vacuum injection method into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.6 degrees, whereas the pretilt angle after the irradiation was 87.0 degrees, which was a pretilt. The content of the compound represented by the general formula (I-2) contained in the device was analyzed by liquid chromatographic analysis, but was below the detection limit. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-2) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Example 12)
Compound selected from general formula (II), compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) As an example containing a compound selected from the following, a liquid crystal composition LC-6 having the following components was prepared.
上記液晶組成物LC−6の物性を表7に示す。 Table 7 shows the physical properties of the liquid crystal composition LC-6.
液晶組成物LC−6 99.7%に対して、一般式(I-37)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−12を調製した。CLC−12をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.8度であったのに対して、照射後のプレチルト角は86.5度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-37)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-37)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例13)
一般式(II)から選ばれる化合物、一般式(IIIa)、一般式(IIIb)及び一般式(IIIc)から選ばれる化合物又は、一般式(IVa)、一般式(IVb)及び一般式(IVc)から選ばれる化合物を含有した実例として以下のような構成成分の液晶組成物LC−7調製した。A polymerizable liquid crystal composition CLC-12 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-37) to 99.7% of the liquid crystal composition LC-6 and uniformly dissolving it. . CLC-12 was injected by a vacuum injection method into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.8 degrees, whereas the pretilt angle after the irradiation was 86.5 degrees, and a pretilt was given. The content of the compound represented by the general formula (I-37) contained in the element was analyzed by liquid chromatographic analysis, but was below the detection limit. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-37) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Example 13)
Compound selected from general formula (II), compound selected from general formula (IIIa), general formula (IIIb) and general formula (IIIc), or general formula (IVa), general formula (IVb) and general formula (IVc) As an example containing a compound selected from the following, a liquid crystal composition LC-7 having the following components was prepared.
上記液晶組成物LC−7物性を表8示す。 Table 8 shows the physical properties of the liquid crystal composition LC-7.
液晶組成物LC−7 99.7%に対して、一般式(I-37)で示される重合性化合物を0.3%添加し均一溶解することにより重合性液晶組成物CLC−13を調製した。CLC−13をセルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数1KHzで1.8Vの矩形波を印加しながら、320nm以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が10mW/cm2となるように調整して600秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。素子の紫外線照射前のプレチルト角は、89.7度であったのに対して、照射後のプレチルト角は86.6度とプレチルトが付与されていた。液体クロマトグラフ分析により、素子中に含有する一般式(I-37)で示される化合物の含有量を分析したが、検出限界以下であった。これにより、一般式(I-37)で示される重合性化合物は、重合開始剤を使用することなく重合することができ、かつ重合後に残存する未重合物が検出限界以下であることを確認した。
(実施例14及び比較例2)
実施例1〜13及び比較例1で作製した重合後の液晶表示素子を電圧印加し、経過時間と焼き付きの様子を目視観察した。(○は変化は見られないことを表す。×は焼き付きが見られ、×の数が多いほど程度が悪いことを表す。)A polymerizable liquid crystal composition CLC-13 was prepared by adding 0.3% of the polymerizable compound represented by the general formula (I-37) to 99.7% of the liquid crystal composition LC-7 and uniformly dissolving it. . CLC-13 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. The pretilt angle before the ultraviolet irradiation of the element was 89.7 degrees, whereas the pretilt angle after the irradiation was 86.6 degrees, and a pretilt was given. The content of the compound represented by the general formula (I-37) contained in the element was analyzed by liquid chromatographic analysis, but was below the detection limit. Thereby, it was confirmed that the polymerizable compound represented by the general formula (I-37) can be polymerized without using a polymerization initiator, and the unpolymerized product remaining after the polymerization is below the detection limit. .
(Example 14 and Comparative Example 2)
A voltage was applied to the liquid crystal display elements after polymerization prepared in Examples 1 to 13 and Comparative Example 1, and the elapsed time and the state of image sticking were visually observed. (○ indicates that no change is observed. × indicates burn-in, and the greater the number of ×, the worse the degree.)
比較例1で作製した液晶表示素子は表示後48時間で焼き付きが発生し、168時間後には、ほぼ全面に渡り表示不良が見られた。これに対し実施例1〜13で作製した液晶表示素子では、500時間経過後でも、良好な表示状態を維持した。これにより、本願発明化合物のように重合性材料がすべて重合し消費された液晶表示素子の高い信頼性が確認できた。 The liquid crystal display device manufactured in Comparative Example 1 burned in 48 hours after display, and display defects were observed over almost the entire surface after 168 hours. On the other hand, in the liquid crystal display element produced in Examples 1-13, the favorable display state was maintained even after 500 hours passed. Thereby, the high reliability of the liquid crystal display element in which all of the polymerizable material was polymerized and consumed like the compound of the present invention was confirmed.
液晶表示素子用の液晶材料として有用である。 It is useful as a liquid crystal material for liquid crystal display elements.
Claims (8)
S11は、炭素原子数1〜12のアルキレン基、又は単結合を表し、該アルキレン基中のメチレン基は酸素原子同士が直接結合しないものとして酸素原子、−COO−、−OCO−、又は−OCOO−に置き換えられても良い、
Z11は、−S12−R12
(式中、R12は独立してR11と同じ意味を表し、S12は独立してS11と同じ意味を表す。)を表し、
X11、X12、X13及びX14は、お互い独立して水素原子、アルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲン化アルコキシ基、ハロゲン、シアノ基、又はニトロ基を表し、
L11、L12、及びL14はお互い独立して、単結合、−O−、−S−、−CH2−、−OCH2−、−CH2O−、−CO−、−C2H4−、―COO−、−OCO−、−OCOOCH2−、−CH2OCOO−、−CO−NRa−、−NRa−CO−、−SCH2−、−CH2S−、―CH=CH−COO−、−COO―CH=CH−、−OCO−CH=CH−、−CH=CH−OCO−、―COOC2H4−、―OCOC2H4−、―C2H4OCO−、―C2H4COO−、−OCOCH2−、―CH2COO−、−CH=CH−、−CF=CH−、−CH=CF−、−CF2−、−CF2O−、−OCF2−、−CF2CH2−、−CH2CF2−、−CF2CF2−又は−C≡C−を表し(式中、Raは炭素原子数1〜4のアルキル基を表す。)、
L13は、―CH=CH−COO−、―CH=CH−OCO−、―COO−CH=CH−又は―OCO−CH=CH−を表し、
M11、及びM12は、お互い独立して1,4−フェニレン基、ピリジン−2,5−ジイル基、ピリミジン−2,5−ジイル基又はナフタレン−2,6−ジイル基を表し、M11、M12は、お互い独立して無置換であるか又はこれらの基中に含まれる水素原子がフッ素原子、塩素原子、シアノ基、又は炭素原子数1〜8のアルキル基、ハロゲン化アルキル基、ハロゲン化アルコキシ基、アルコキシ基、又はニトロ基に置換されていても良く、
mは0又は1を表し、nは、1、2又は3を表し、nが2又は3を表す場合、2個又は3個存在するM12は同一であっても異なっていても良く、2個又は3個存在するL14は同一であっても異なっていても良い。)で表される重合性化合物から選ばれる一種又は二種以上の化合物を含有し、第二成分として、一般式(II)
M21、M22及びM23はお互い独立して
(a) トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置き換えられてもよい)、
(b) 1,4-フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は窒素原子に置き換えられてもよい)、3-フルオロ-1,4-フェニレン基、3,5-ジフルオロ-1,4-フェニレン基、及び
(c) 1,4-シクロヘキセニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ピペリジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基及び1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基
からなる群より選ばれる基を表し、
oは0、1又は2を表し、
L21、及びL22はお互い独立して単結合、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−、−CH=CH−、−CH=N−N=CH−又は−C≡C−を表し、L22が複数存在する場合は、同一でも良く異なっていても良く、M23が複数存在する場合は、同一でも良く異なっていても良い。)で表される化合物を一種又は二種以上含有し、第三成分として、一般式(IVa)、一般式(IVb)及び一般式(IVc)
M41、M42、M43、M44、M45、M46、M47、M48、及びM49はお互い独立して、
(d) トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は−O−又は−S−に置き換えられてもよい)、
(e) 1,4-フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は窒素原子に置き換えられてもよい)及び、
(f) 1,4-シクロヘキセニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ピペリジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基及びデカヒドロナフタレン-2,6-ジイル基
からなる群より選ばれる基であり、上記の基(d)、基(e)又は基(f)に含まれる水素原子はそれぞれシアノ基、フッ素原子、トリフルオロメチル基、トリフルオロメトキシ基又は塩素原子で置換されていても良く、
L41、L42、L43、L44、L45、L46、L47、L48、及びL49はお互い独立して単結合、−COO−、−OCO−、−CH2CH2−、−(CH2)4−、−OCH2−、−CH2O−、−OCF2−、−CF2O−又は−C≡C−を表し、M42、M43、M45、M46、M48、M49、L41、L43、L44、L46、L47及び/又はL49が複数存在する場合は、それらは同一でも良く異なっていても良く、
X41、X42はお互い独立してトリフルオロメチル基、トリフルオロメトキシ基又はフッ素原子を表し、X43、X44、X45、X46、X47、及びX48はお互い独立して水素原子、トリフルオロメチル基、トリフルオロメトキシ基又はフッ素原子を表すが、X41及びX42の何れか一つはフッ素原子を表し、X43、X44、及びX45の何れか一つはフッ素原子を表し、X46、X47、及びX48の何れか一つはフッ素原子を表すが、X46、及びX47、は同時にフッ素原子を表すことはなく、X46、及びX48は同時にフッ素原子を表すことはない、
Gはメチレン基又は−O−を表し、
u、v、w、x、y、及びzはお互い独立して、0、1又は2を表すが、u+v、w+x及びy+zは2以下である。)で表される化合物からなる群から選ばれる化合物を一種又は二種以上含有し、液晶組成物中の重合性化合物が重合することにより液晶配向能が付与され、液晶組成物の複屈折を利用して光の透過光量を制御する液晶表示素子に使用される液晶組成物。As the first component, the general formula (I)
S 11 represents an alkylene group having 1 to 12 carbon atoms or a single bond, and the methylene group in the alkylene group is an oxygen atom, —COO—, —OCO—, or — May be replaced by OCOO-,
Z 11 represents -S 12 -R 12
(Wherein R 12 independently represents the same meaning as R 11, and S 12 independently represents the same meaning as S 11 ),
X 11 , X 12 , X 13 and X 14 each independently represent a hydrogen atom, an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen, a cyano group, or a nitro group,
L 11 , L 12 , and L 14 are each independently a single bond, —O—, —S—, —CH 2 —, —OCH 2 —, —CH 2 O—, —CO—, —C 2 H. 4 -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - COO- CH = CH -, - OCO-CH = CH -, - CH = CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO- , —C 2 H 4 COO—, —OCOCH 2 —, —CH 2 COO—, —CH═CH—, —CF═CH—, —CH═CF—, —CF 2 —, —CF 2 O—, — OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 - or -C≡ - it represents, (wherein, R a represents an alkyl group having 1 to 4 carbon atoms.)
L 13 represents —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH— or —OCO—CH═CH—,
M 11, and M 12 represent independently of one another, are a 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group or a naphthalene-2,6-diyl group, M 11 , M 12 are each independently unsubstituted or a hydrogen atom contained in these groups is a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group, It may be substituted with a halogenated alkoxy group, an alkoxy group, or a nitro group,
m represents 0 or 1, n represents 1, 2 or 3, and when n represents 2 or 3, two or three M 12 may be the same or different. One or three L 14 may be the same or different. ) Containing one or more compounds selected from the polymerizable compounds represented by formula (II) as the second component
M 21 , M 22 and M 23 are independent of each other
(a) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by -O- or -S-) ),
(b) 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom), 3-fluoro-1 , 4-phenylene group, 3,5-difluoro-1,4-phenylene group, and
(c) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 -Represents a group selected from the group consisting of -diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group,
o represents 0, 1 or 2;
L 21 and L 22 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— , —CH═CH—, —CH═N—N═CH— or —C≡C—, and when there are a plurality of L 22 s , they may be the same or different, and there are a plurality of M 23 s. May be the same or different. 1 or 2 or more compounds represented by the general formula (IVa), general formula (IVb) and general formula (IVc)
M 41 , M 42 , M 43 , M 44 , M 45 , M 46 , M 47 , M 48 , and M 49 are independent of each other.
(d) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by -O- or -S-) ),
(e) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom);
(f) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3,4 -A group selected from the group consisting of a tetrahydronaphthalene-2,6-diyl group and a decahydronaphthalene-2,6-diyl group, and is included in the above group (d), group (e) or group (f) Each hydrogen atom may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
L 41 , L 42 , L 43 , L 44 , L 45 , L 46 , L 47 , L 48 , and L 49 are each independently a single bond, —COO—, —OCO—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— or —C≡C— represents M 42 , M 43 , M 45 , M 46 , When there are a plurality of M 48 , M 49 , L 41 , L 43 , L 44 , L 46 , L 47 and / or L 49 , they may be the same or different,
X 41 and X 42 each independently represents a trifluoromethyl group, a trifluoromethoxy group or a fluorine atom, and X 43 , X 44 , X 45 , X 46 , X 47 and X 48 are each independently a hydrogen atom. , A trifluoromethyl group, a trifluoromethoxy group, or a fluorine atom, wherein any one of X 41 and X 42 represents a fluorine atom, and any one of X 43 , X 44 , and X 45 represents a fluorine atom Any one of X 46 , X 47 and X 48 represents a fluorine atom, but X 46 and X 47 do not represent a fluorine atom at the same time, and X 46 and X 48 represent fluorine at the same time. Never represent an atom,
G represents a methylene group or —O—;
u, v, w, x, y, and z each independently represent 0, 1, or 2, but u + v, w + x, and y + z are 2 or less. 1) or two or more compounds selected from the group consisting of the compounds represented by formula (1), and the polymerizable compound in the liquid crystal composition is polymerized to impart liquid crystal alignment ability and utilize the birefringence of the liquid crystal composition. Liquid crystal composition used for a liquid crystal display element for controlling the amount of transmitted light.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010541623A JP4803320B2 (en) | 2009-04-14 | 2010-04-01 | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009097946 | 2009-04-14 | ||
JP2009097946 | 2009-04-14 | ||
PCT/JP2010/056009 WO2010119779A1 (en) | 2009-04-14 | 2010-04-01 | Liquid crystal composition containing polymerizable compound and liquid crystal display element using same |
JP2010541623A JP4803320B2 (en) | 2009-04-14 | 2010-04-01 | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011103538A Division JP5640883B2 (en) | 2009-04-14 | 2011-05-06 | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP4803320B2 true JP4803320B2 (en) | 2011-10-26 |
JPWO2010119779A1 JPWO2010119779A1 (en) | 2012-10-22 |
Family
ID=42982441
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2010541623A Active JP4803320B2 (en) | 2009-04-14 | 2010-04-01 | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same |
JP2011103538A Active JP5640883B2 (en) | 2009-04-14 | 2011-05-06 | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011103538A Active JP5640883B2 (en) | 2009-04-14 | 2011-05-06 | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same |
Country Status (7)
Country | Link |
---|---|
US (1) | US8603358B2 (en) |
EP (1) | EP2420548B1 (en) |
JP (2) | JP4803320B2 (en) |
KR (1) | KR101605038B1 (en) |
CN (1) | CN102395651B (en) |
TW (1) | TWI500742B (en) |
WO (1) | WO2010119779A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011202168A (en) * | 2009-04-14 | 2011-10-13 | Dic Corp | Liquid crystal composition containing polymerizable compound and liquid crystal display element using the same |
JP5376088B2 (en) * | 2011-09-27 | 2013-12-25 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
JP7472606B2 (en) | 2020-04-01 | 2024-04-23 | Dic株式会社 | Liquid crystal composition and liquid crystal display device |
JP7472607B2 (en) | 2020-04-01 | 2024-04-23 | Dic株式会社 | Liquid crystal composition and liquid crystal display device |
Families Citing this family (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008064171A1 (en) | 2008-12-22 | 2010-07-01 | Merck Patent Gmbh | Liquid crystalline medium |
JP5545516B2 (en) * | 2009-09-25 | 2014-07-09 | Dic株式会社 | Polymerizable compound |
JP5720919B2 (en) * | 2010-02-04 | 2015-05-20 | Dic株式会社 | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same |
WO2011132451A1 (en) * | 2010-04-22 | 2011-10-27 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
TWI506124B (en) * | 2010-05-28 | 2015-11-01 | Jnc Corp | Liquid crystal composition and liquid crystal display element |
EP2626402B1 (en) * | 2010-10-04 | 2019-07-10 | JNC Corporation | Liquid crystal composition and liquid crystal display element |
CN104498052A (en) | 2011-04-06 | 2015-04-08 | Dic株式会社 | Nematic Liquid Crystal Composition, Liquid Crystal Display Element Using Same |
TWI577783B (en) | 2011-08-11 | 2017-04-11 | 迪愛生股份有限公司 | Liquid crystal composition containing polymerizable compound and liquid crystal display element using the same |
US9073850B2 (en) | 2011-11-24 | 2015-07-07 | Jnc Corporation | Polymerizable compound |
JP6136932B2 (en) * | 2011-11-24 | 2017-05-31 | Jnc株式会社 | Polymerizable compound |
TW201323588A (en) | 2011-12-05 | 2013-06-16 | Jnc Corp | Liquid crystal composition and usage thereof, and liquid crystal display element |
DE102012024126A1 (en) | 2011-12-20 | 2013-06-20 | Merck Patent Gmbh | Liquid crystalline medium |
EP2701003B1 (en) * | 2012-03-30 | 2017-03-01 | DIC Corporation | Liquid crystal display element |
TWI635164B (en) * | 2012-04-24 | 2018-09-11 | 迪愛生股份有限公司 | Liquid crystal composition containing polymerizable compound and liquid crystal display element using same |
US8961823B2 (en) * | 2012-07-05 | 2015-02-24 | Jnc Corporation | Polymerizable compound, liquid crystal composition and liquid crystal display device |
US9150787B2 (en) * | 2012-07-06 | 2015-10-06 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
CN102863970A (en) * | 2012-09-21 | 2013-01-09 | 深圳市华星光电技术有限公司 | Liquid-crystal medium mixture and liquid-crystal display utilizing same |
CN102863968A (en) * | 2012-09-21 | 2013-01-09 | 深圳市华星光电技术有限公司 | Liquid crystal medium mixture and liquid crystal display using liquid crystal medium mixture |
WO2014065231A1 (en) * | 2012-10-24 | 2014-05-01 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
TWI606113B (en) * | 2013-02-06 | 2017-11-21 | Dainippon Ink & Chemicals | Liquid crystal display element and its manufacturing method |
KR101691101B1 (en) * | 2013-03-21 | 2016-12-29 | 디아이씨 가부시끼가이샤 | Polymerizable compound-containing liquid crystal composition and liquid crystal display element using same |
JP6153999B2 (en) * | 2013-03-21 | 2017-06-28 | Dic株式会社 | Polymerizable compound-containing liquid crystal composition and liquid crystal display device using the same |
CN105518035B (en) * | 2013-11-29 | 2017-05-03 | Dic株式会社 | Compound, polymer, liquid crystal alignment film, liquid crystal display element, and optical anisotropic body |
CN105899644A (en) * | 2014-01-06 | 2016-08-24 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display device using same |
WO2015114864A1 (en) * | 2014-01-30 | 2015-08-06 | 公立大学法人兵庫県立大学 | Photoreactive liquid crystal composition, display element, optical element, method for manufacturing display element, and method for manufacturing optical element |
KR101849961B1 (en) | 2014-05-13 | 2018-04-19 | 디아이씨 가부시끼가이샤 | Nematic liquid crystal composition and liquid crystal display element using same |
WO2015194632A1 (en) * | 2014-06-19 | 2015-12-23 | Dic株式会社 | Polymerizable-monomer-containing liquid crystal composition and liquid crystal display element using same |
US9994772B2 (en) * | 2014-07-15 | 2018-06-12 | Dic Corporation | Liquid crystal display device |
US10414980B2 (en) * | 2014-07-29 | 2019-09-17 | Dic Corporation | Liquid-crystal display |
TW201632608A (en) * | 2014-12-12 | 2016-09-16 | Dainippon Ink & Chemicals | Liquid crystal display element and method of manufacturing the same |
TW201632609A (en) * | 2014-12-12 | 2016-09-16 | Dainippon Ink & Chemicals | Liquid crystal display element and method of manufacturing the same |
CN111849508A (en) * | 2014-12-25 | 2020-10-30 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
KR102272215B1 (en) * | 2015-01-13 | 2021-07-02 | 삼성디스플레이 주식회사 | Liquid crystal composition, liquid crystal display including the same, and manufacturing method thereof |
CN107434973B (en) * | 2016-05-27 | 2023-01-10 | 江苏和成显示科技有限公司 | Liquid crystal compound and composition and application thereof |
US20190292461A1 (en) * | 2016-12-06 | 2019-09-26 | Jnc Corporation | Liquid crystal composite and liquid crystal dimming device |
CN108169960A (en) * | 2016-12-07 | 2018-06-15 | 捷恩智株式会社 | Phase difference film and the polymerizable mesogenic film class using polymerizable liquid crystal compound |
DE102018000075A1 (en) * | 2017-02-03 | 2018-08-09 | Merck Patent Gmbh | Liquid crystalline compounds |
CN109575939A (en) * | 2017-09-28 | 2019-04-05 | 江苏和成显示科技有限公司 | Liquid-crystal composition and its liquid crystal display device |
CN109575950B (en) * | 2017-09-28 | 2021-07-06 | 江苏和成显示科技有限公司 | Polymerizable liquid crystal composition and display device thereof |
CN108130102A (en) * | 2017-12-28 | 2018-06-08 | 中节能万润股份有限公司 | A kind of preparation method containing lateral fluorochemical monomer liquid crystal |
TW202034045A (en) * | 2018-10-02 | 2020-09-16 | 日商Dic股份有限公司 | Liquid crystal composition using alignment assistant, liquid crystal display element and method for producing same |
CN112789344A (en) * | 2018-12-12 | 2021-05-11 | Dic株式会社 | Polymerizable compound-containing liquid crystal composition, liquid crystal display element, and polymerizable compound |
CN115785971A (en) * | 2022-12-07 | 2023-03-14 | Tcl华星光电技术有限公司 | Liquid crystal composition and liquid crystal display panel |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000109843A (en) * | 1998-10-08 | 2000-04-18 | Dainippon Ink & Chem Inc | Nematic liquid crystal composition and liquid crystal display device using the same |
JP2000119653A (en) * | 1998-10-16 | 2000-04-25 | Dainippon Ink & Chem Inc | Nematic liquid crystal composition and liquid crystal display using same |
JP2004131704A (en) * | 2002-07-06 | 2004-04-30 | Merck Patent Gmbh | Liquid crystal medium |
JP2005120091A (en) * | 2003-10-17 | 2005-05-12 | Merck Patent Gmbh | Polymerizable cinnamate having substituent in side position |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5223959A (en) | 1989-07-17 | 1993-06-29 | Polytronix, Inc. | Red, blue and green serial encapsulated liquid crystal display and driving method |
US5056898A (en) | 1989-07-17 | 1991-10-15 | Polytronix, Inc. | Reverse mode microdroplet liquid crystal light shutter displays |
AU6132796A (en) * | 1995-06-23 | 1997-01-22 | Zylepsis Limited | Chemical compounds and methods of production thereof |
JP4175826B2 (en) * | 2002-04-16 | 2008-11-05 | シャープ株式会社 | Liquid crystal display |
JP4437408B2 (en) | 2004-02-04 | 2010-03-24 | 富士通株式会社 | Liquid crystal display device and manufacturing method thereof |
DE502007004908D1 (en) | 2006-10-12 | 2010-10-14 | Merck Patent Gmbh | liquid-crystal display |
JP5143475B2 (en) * | 2007-05-17 | 2013-02-13 | Dic株式会社 | Nematic liquid crystal composition and bistable nematic liquid crystal display device |
JP4803320B2 (en) * | 2009-04-14 | 2011-10-26 | Dic株式会社 | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same |
JP5720919B2 (en) * | 2010-02-04 | 2015-05-20 | Dic株式会社 | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same |
-
2010
- 2010-04-01 JP JP2010541623A patent/JP4803320B2/en active Active
- 2010-04-01 US US13/264,034 patent/US8603358B2/en active Active
- 2010-04-01 EP EP10764364.5A patent/EP2420548B1/en active Active
- 2010-04-01 WO PCT/JP2010/056009 patent/WO2010119779A1/en active Application Filing
- 2010-04-01 KR KR1020117020258A patent/KR101605038B1/en active IP Right Grant
- 2010-04-01 CN CN201080016504.2A patent/CN102395651B/en active Active
- 2010-04-12 TW TW099111202A patent/TWI500742B/en active
-
2011
- 2011-05-06 JP JP2011103538A patent/JP5640883B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000109843A (en) * | 1998-10-08 | 2000-04-18 | Dainippon Ink & Chem Inc | Nematic liquid crystal composition and liquid crystal display device using the same |
JP2000119653A (en) * | 1998-10-16 | 2000-04-25 | Dainippon Ink & Chem Inc | Nematic liquid crystal composition and liquid crystal display using same |
JP2004131704A (en) * | 2002-07-06 | 2004-04-30 | Merck Patent Gmbh | Liquid crystal medium |
JP2005120091A (en) * | 2003-10-17 | 2005-05-12 | Merck Patent Gmbh | Polymerizable cinnamate having substituent in side position |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011202168A (en) * | 2009-04-14 | 2011-10-13 | Dic Corp | Liquid crystal composition containing polymerizable compound and liquid crystal display element using the same |
JP5376088B2 (en) * | 2011-09-27 | 2013-12-25 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
JP7472606B2 (en) | 2020-04-01 | 2024-04-23 | Dic株式会社 | Liquid crystal composition and liquid crystal display device |
JP7472607B2 (en) | 2020-04-01 | 2024-04-23 | Dic株式会社 | Liquid crystal composition and liquid crystal display device |
Also Published As
Publication number | Publication date |
---|---|
US20120097895A1 (en) | 2012-04-26 |
KR101605038B1 (en) | 2016-03-21 |
JPWO2010119779A1 (en) | 2012-10-22 |
JP2011202168A (en) | 2011-10-13 |
TWI500742B (en) | 2015-09-21 |
JP5640883B2 (en) | 2014-12-17 |
CN102395651B (en) | 2014-06-25 |
CN102395651A (en) | 2012-03-28 |
EP2420548A1 (en) | 2012-02-22 |
US8603358B2 (en) | 2013-12-10 |
EP2420548B1 (en) | 2018-07-04 |
KR20120013303A (en) | 2012-02-14 |
TW201100525A (en) | 2011-01-01 |
EP2420548A4 (en) | 2017-05-03 |
WO2010119779A1 (en) | 2010-10-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4803320B2 (en) | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same | |
JP5720919B2 (en) | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same | |
JP5573011B2 (en) | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same | |
JP5743132B2 (en) | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same | |
JP5445715B2 (en) | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same | |
JP6508250B2 (en) | Liquid crystal composition containing a polymerizable compound and liquid crystal display device using the same | |
JP4840543B2 (en) | Polymerizable compound-containing liquid crystal composition and liquid crystal display device using the same | |
JP5692565B2 (en) | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same | |
JP5743129B2 (en) | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same | |
JP5699518B2 (en) | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the same | |
JP5751466B2 (en) | Polymerizable compound-containing liquid crystal composition and liquid crystal display device using the same | |
JP5712551B2 (en) | Polymerizable compound-containing liquid crystal composition and liquid crystal display device using the same | |
JP5712552B2 (en) | Polymerizable compound-containing liquid crystal composition and liquid crystal display device using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110712 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110725 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4803320 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140819 Year of fee payment: 3 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |